Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

(Table 2, page 50) Toolik lake sediment chemistry (0-1 cm interval)

The sediments within Toolik Lake in arctic Alaska are characterized by extremely low rates of organic matter sedimentation and unusually high concentrations of iron and manganese. Pore water and solid phase measurements of iron, manganese, trace metals, carbon, nitrogen, phosphorus, and sulfur are consistent with the hypothesis that the reduction of organic matter by iron and manganese is the most important biogeochemical reaction within the sediment. Very low rates of dissolved oxygen consumption by the sediments result in an oxidizing environment at the sediment-water interface. This results in high retention of upwardly-diffusing iron and manganese and the formation of metal-enriched sediment. Phosphate in sediment pore waters is strongly adsorbed by the metal-enriched phases. Consequently, fluxes of phosphorus from the sediments to overlying waters are very small and contribute to the oligotrophic nature of the Toolik Lake aquatic system. Toolik Lake contains an unusual type of lacustrine sediment, and in many ways the sediments are similar to those found in oligotrophic oceanic environments.

High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

Measurements of gastropods shell sizes from 23 fossil and extant long-lived lakes

Aim: To investigate shell size variation among gastropod faunas of fossil and recent long-lived European lakes and discuss potential underlying processes. Location: 23 long-lived lakes of the Miocene to Recent of Europe. Methods: Based on a dataset of 1412 species of both fossil and extant lacustrine gastropods, we assessed differences in shell size in terms of characteristics of the faunas (species richness, degree of endemism, differences in family composition) and the lakes (surface area, latitude and longitude of lake centroid, distance to closest neighbouring lake) using multiple and linear regression models. Because of a strong species-area relationship, we used resampling to determine whether any observed correlation is driven by that relationship. Results: The regression models indicated size range expansion rather than unidirectional increase or decrease as the dominant pattern of size evolution. The multiple regression models for size range and maximum and minimum size were statistically significant, while the model with mean size was not. Individual contributions and linear regressions indicated species richness and lake surface area as best predictors for size changes. Resampling analysis revealed no significant effects of species richness on the observed patterns. The correlations are comparable across families of different size classes, suggesting a general pattern. Main conclusions: Among the chosen variables, species richness and lake surface area are the most robust predictors of shell size in long-lived lake gastropods. Although the most outstanding and attractive examples for size evolution in lacustrine gastropods derive from lakes with extensive durations, shell size appears to be independent of the duration of the lake as well as longevity of a species. The analogue of long-lived lakes as 'evolutionary islands' does not hold for developments of shell size because different sets of parameters predict size changes.

Phenotypic evolution in a fossil gastropod species lineage: evidence for adaptive radiation?

Detecting speciation in the fossil record is a particularly challenging matter. Palaeontologists are usually confronted with poor preservation and limited knowledge on the palaeoenvironment. Even in the contrary case of adequate preservation and information, the linkage of pattern to process is often obscured by insufficient temporal resolution. Consequently, reliable documentations of speciation in fossils with discussions on underlying mechanisms are rare. Here we present a well-resolved pattern of morphological evolution in a fossil species lineage of the gastropod Melanopsis in the long-lived Lake Pannon. These developments are related to environmental changes, documented by isotope and stratigraphical data. After a long period of stasis, the ancestral species experiences a phenotypic change expressed as shift and expansion of the morphospace. The appearance of several new phenotypes along with changes in the environment is interpreted as adaptive radiation. Lake-level high stands affect distribution and availability of habitats and, as a result of varied functional demands on shell geometry, the distribution of phenotypes. The on-going divergence of the morphospace into two branches argues for increasing reproductive isolation, consistent with the model of ecological speciation. In the latest phase, however, progressively unstable conditions restrict availability of niches, allowing survival of one branch only.

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2008)

This data set contains measurements of total nitrogen 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. Soil sampling and analysis: Stratified soil sampling was performed in April 2008 to a depth of 30 cm. Three independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were segmented to a depth resolution of 5 cm in the field, giving six depth subsamples per core, and made into composite samples per depth. Sampling locations were less than 30 cm apart from sampling locations in other years. Samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Sea surface fugacity of carbon dioxide measurements in the Pacific ocean

As part of the JGOFS field program, extensive CO2 partial-pressure measurements were made in the atmosphere and in the surface waters of the equatorial Pacific from 1992 to 1999. For the first time, we are able to determine how processes occurring in the western portion of the equatorial Pacific impact the sea-air fluxes of CO2 in the central and eastern regions. These 8 years of data are compared with the decade of the 1980s. Over this period, surface-water pCO2 data indicate significant seasonal and interannual variations. The largest decreases in fluxes were associated with the 1991-94 and 1997-98 El Niño events. The lower sea-air CO2 fluxes during these two El Niño periods were the result of the combined effects of interconnected large-scale and locally forced physical processes: (1) development of a low-salinity surface cap as part of the formation of the warm pool in the western and central equatorial Pacific, (2) deepening of the thermocline by propagating Kelvin waves in the eastern Pacific, and (3) the weakening of the winds in the eastern half of the basin. These processes serve to reduce pCO2 values in the central and eastern equatorial Pacific towards near-equilibrium values at the height of the warm phase of ENSO. In the western equatorial Pacific there is a small but significant increase in seawater pCO2 during strong El Niño events (i.e., 1982-83 and 1997-98) and little or no change during weak El Niño events (1991-94). The net effect of these interannual variations is a lower-than-normal CO2 flux to the atmosphere from the equatorial Pacific during El Niño. The annual average fluxes indicate that during strong El Niños the release to the atmosphere is 0.2-0.4 Pg C/yr compared to 0.8-1.0 Pg C/yr during non-El Niño years.

Total nitrogen from solid phase in the Jena Experiment (Block 2 Main Experiment up to 100cm depth, year 2002)

This data set contains measurements of total nitrogen 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. Soil sampling and analysis: Stratified soil sampling to a depth of 1m was performed before sowing in April 2002. Three independent samples per plot were taken of all plots in block 2 using a motor-driven soil column cylinder (Cobra, Eijkelkamp, 8.3 cm in diameter). Soil samples were dried at 40°C and segmented to a depth resolution of 5 cm giving 20 depth subsamples per core. All samples were analyzed independently. All soil samples were passed through a sieve with a mesh size of 2 mm. Rarely present visible plant remains were removed using tweezers. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Total nitrogen from solid phase in the Jena Experiment (Main Experiment up to 30cm depth, year 2004)

This data set contains measurements of total nitrogen 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. Soil sampling and analysis: Stratified soil sampling was performed in April 2004 to a depth of 30 cm. Three independent samples per plot were taken using a split tube sampler with an inner diameter of 4.8 cm (Eijkelkamp Agrisearch Equipment, Giesbeek, the Netherlands). Soil samples were segmented to a depth resolution of 5 cm in the field, giving six depth subsamples per core, and made into composite samples per depth. Sampling locations were less than 30 cm apart from sampling locations in other years. Samples were dried at 40°C. All soil samples were passed through a sieve with a mesh size of 2 mm. Because of much higher proportions of roots in the soil, the samples were further sieved to 1 mm according to common root removal methods. No additional mineral particles were removed by this procedure. Total nitrogen concentration was analyzed on ball-milled subsamples (time 4 min, frequency 30 s-1) by an elemental analyzer at 1150°C (Elementaranalysator vario Max CN; Elementar Analysensysteme GmbH, Hanau, Germany).

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

Bulk rock magnetic measurements and thermomagnetic analyses of sediment core GeoB4901-8 from the southeastern flank of the Niger deep-sea fan

Diagenesis has extensively affected the magnetic mineral inventory of organic-rich late Quaternary sediments in the Niger deep-sea fan. Changes in concentration, grain size, and coercivity document modifications of the primary magnetic mineral assemblages at two horizons. The first front, the modern iron redox boundary, is characterized by a drastic decline in magnetic mineral content, coarsening of the grain size spectrum, and reduction in coercivity. Beneath a second front, the transition from the suboxic to the sulfidic anoxic domain, a further but less pronounced decrease in concentration and bulk grain size occurs. Finer grains and higher coercive magnetic constituents substantially increase in the anoxic environment. Low- and high-temperature experiments were performed on bulk sediments and on extracts which have also been examined by X-ray diffraction. Thermomagnetic analyses proved ferrimagnetic titanomagnetites of terrigenous provenance as the principal primary magnetic mineral components. Their broad range of titanium contents reflects the volcanogenic traits of the Niger River drainage areas. Diagenetic alteration is not only a grain size selective process but also critically depends on titanomagnetite composition. Low-titanium compounds are less resistant to diagenetic dissolution. Intermediate titanium content titanomagnetite thus persists as the predominant magnetic mineral fraction in the sulfidic anoxic sediments. At the Fe redox boundary, precipitation of authigenic, possibly bacterial, magnetite is documented. The presence of hydrogen sulfide in the pore water suggests a formation of secondary magnetic iron sulfides in the anoxic domain. Grain size-specific data argue for a gradual development of a superparamagnetic and single-domain iron sulfide phase in this milieu, most likely greigite.

Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.