Sediment and organic matter properties, and molecular formula from sampling locations in the Northern Black Sea

Remineralization of organic matter in reactive marine sediments releases nutrients and dissolved organic matter (DOM) into the ocean. Here we focused on the molecular-level characterization of DOM by high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sediment pore waters and bottom waters from contrasting redox regimes in the northern Black Sea with particular emphasis on nitrogen-bearing compounds to derive an improved understanding of the molecular transformations involved in nitrogen release. The number of nitrogen-bearing molecules is generally higher in pore waters than in bottom waters. This suggests intensified degradation of nitrogen-bearing precursor molecules such as proteins in anoxic sediments: No significant difference was observed between sediments deposited under oxic vs anoxic conditions (average O/C ratios of 0.55) suggesting that the different organic matter quality induced by contrasting redox conditions does not impact protein diagenesis in the subseafloor. Compounds in the pore waters were on average larger, less oxygenated, and had a higher number of unsaturations. Applying a mathematical model, we could show that the assemblages of nitrogen-bearing molecular formulas are potential products of proteinaceous material that was transformed by the following reactions: (a) hydrolysis and deamination, both reducing the molecular size and nitrogen content of the products and intermediates; (b) oxidation and hydration of the intermediates; and (c) methylation and dehydration.

(Table T1) Permeabilities and bulk properties of ODP Hole 191-1179C

One of the objectives of drilling at Site 1179 was to search for microbes or biochemical evidence of microbial activity as part of the ongoing exploration of the depth and extent of the deep biosphere. The existence of living microbes has not been confirmed, but the chemistry of pore waters from the site, such as sulfate and ammonium profiles, is consistent with sulfate reduction and nitrification by anaerobic bacteria. However, chemical profiles are affected by the movement of molecules and ions through porous sediments by diffusion and advection. Permeability is thus an important consideration in the interpretation of pore water chemistry profiles. Moreover, diatomaceous sediments have some unique and, as yet, poorly understood physical properties. The purpose of this research is to measure hydraulic conductivity (permeability) in a suite of sediment samples from Ocean Drilling Program Site 1179 by the transient-pulse method. The sample set consists of four diatom ooze samples from Unit I, one radiolarian ooze sample from Unit II, and one pelagic clay sample from Unit III. The permeability of the clay is 1.92 µd, whereas the permeabilities of the overlying radiolarian and diatom oozes range from 289 to 1604 µd. Among these samples, permeability increases with porosity and grain size, in keeping with the results of previous studies.

Downcore rock-magnetic properties of ICDP Core 5045-1, Lake Ohrid

The bulk magnetic mineral record from Lake Ohrid, spanning the past 637 kyr, reflects large-scale shifts in hydrological conditions, and, superimposed, a strong signal of environmental conditions on glacial-interglacial and millennial timescales. A shift in the formation of early diagenetic ferrimagnetic iron sulfides to siderites is observed around 320 ka. This change is probably associated with variable availability of sulfide in the pore water. We propose that sulfate concentrations were significantly higher before ~320 ka, due to either a higher sulfate flux or lower dilution of lake sulfate due to a smaller water volume. Diagenetic iron minerals appear more abundant during glacials, which are generally characterized by higher Fe/Ca ratios in the sediments. While in the lower part of the core the ferrimagnetic sulfide signal overprints the primary detrital magnetic signal, the upper part of the core is dominated by variable proportions of high- to low-coercivity iron oxides. Glacial sediments are characterized by high concentration of high-coercivity magnetic minerals (hematite, goethite), which relate to enhanced erosion of soils that had formed during preceding interglacials. Superimposed on the glacial-interglacial behavior are millennial-scale oscillations in the magnetic mineral composition that parallel variations in summer insolation. Like the processes on glacial-interglacial timescales, low summer insolation and a retreat in vegetation resulted in enhanced erosion of soil material. Our study highlights that rock-magnetic studies, in concert with geochemical and sedimentological investigations, provide a multi-level contribution to environmental reconstructions, since the magnetic properties can mirror both environmental conditions on land and intra-lake processes.