Description: Generally, oxidative regeneration of phosphate from anoxic sediments is by microbially mediated sulfate reduction processes. Stoichiometric modelling of such reactions takes into consideration varying proportions of ‘decomposable’ organically bound P to account for the ratios among nutrients in depth-concentration profiles of near-surface sediments. New results of interstitial water composition from sediments underlying the water masses influenced by coastal upwelling of the eastern boundary current system off Peru indicate that dissolution of phosphatic fish debris represents a mechanism for remineralization of phosphate comparable to or larger in magnitude than that by oxidative regeneration of organically bound P. Dissolved interstitial phosphate from fish debris is revealed by an excess amount of phosphate over that predicted from a simple stoichiometric oxidative regeneration model and by anomalously high dissolved interstitial fluoride concentrations. Phosphate flux estimates based on diffusion from the sediment suggest that this mechanism may generate up to 10% of the nutrient pool in the waters of the Peru undercurrent. Partitioning of P among the two sources reveals further that fish debris phosphate is about four times more important than organically bound P in nutrient generation from sediments of the Peru continental margin. Not only does this mechanism of regeneration affect the nutrient cycling but may also control widespread phosphorite formation in this area.

Description: The usually high concentrations of Zn, Pb, Cd, and Cu in the most recently accreted portions of ferromanganese nodules from the western Baltic Sea are thought to reflect increased metal input due to anthropogenic mobilization. If so, the point of increase represents a time horizon within the structure of the nodule. Similar trace metal distributions of radiometrically dated sediments from the same area suggest that the ferromanganese nodules have grown in thickness between 0.02 and 0.16 mm yr−1. From this growth rate anthropogenic Zn flux to the nodule surface was calculated to be 80 mg m−2 yr−1.

Description: A radiotracer technique, employing 27Mg, is used to determine the Mg released by ammonium exchange on undis-solved humic acid in a seawater medium. This new method allows for the measurement of exchangeable Mg on the solid phase surface, which eliminates the problem caused by the high-Mg background in the seawater matrix. The precision calculated from the counting statistics is better than ±2%; the reproducibility among repeated counts ranged from ±1% to ±3%. The higher sensitivity of the method allows for monitoring the MgNH4 exchange at concentrations as low as 30 mM NH4. This is a major improvement relative to the data obtained with the analytical methods used so far, which allow detection of exchangeable Mg only at NH4 concentrations higher than 1 M. The lower experimental concentrations are more in accordance with the natural ammonium levels found in anoxic marine sediments. For the undissolved humic acid used in this experiment, the amount of exchangeable Mg in apparent equilibrium with an ammonium-free seawater matrix was found to be 96.6 ± 0.4 meq/100g. The Mg-NH4 exchange on humic acid in seawater comes to a steady-state value in 〈 18 min. The conditional equilibrium constant obtained for this reaction, Kcond = 0.039 ± 0.001 M−1. The technique can be expanded to other geochemical solid phases in seawater and it can be modified to study the behavior of the major cations by using 24Na, 42K and 49Ca.

Description: Microbial decomposition of organic matter in recent sediments of the Landsort Deep—an anoxic basin of the central Baltic Sea—resulted in the formation of a characteristic assemblage of authigenic mineral precipitates of carbonates, sulfides. phosphates and amorphous silica, The dominant crystalline phases are a mixed Mn-carbonate [(Mn0.85Ca0.10Mg0.05)CO3]. Mn-sulfide [MnS] and Fecarbonate [FeCO3]. Amorphous Fe-sulfide [FeS]. Mn-phosphate [Mn3(PO4)2] and a mixed Fe-Ca-phosphate [(Fe0.86Ca0.14)3(PO4)2] were identified by their chemical compositions only. The variability in composition of these solid phases and their mode of occurrence as a co-existing assemblage constrains the conditions and solution composition from which they precipitated. Estimates of activities for dissolved Fe. Mn. PO4, CO3 and S in equilibrium with such an assemblage are close to those found in recent anoxic interstitial water-sediment systems. It is important to have detailed knowledge of the composition and stability conditions of these solid precipitates in order to refine stoichiometric models of interstitial nutrient regeneration in anoxic sediments.

Description: Surface area measurements as well as organic carbon, nitrogen and phosphorus analyses on various grain size fractions of carbonate mud samples confirm that in natural environments of carbonate deposition, surface sorption processes take place which are similar to those described earlier for dissolved organics and artificially suspended calcite particles in both seawater and synthetic solutions. The specific surface area of the sediment increases from 1.8m2/g for the coarse-grained fraction to 12.5 m2/g for the fine material; likewise organic carbon, nitrogen and phosphorus increase with increasing surface area so that there are 1.20 mg C, 0.175 mg N and 0.06–0.20 mg P associated with every square meter of carbonate surface irrespective of the mineralogy of the sediment particles. It appears that the organic matter in these sediments is similar in composition, structure and quantity to the organic layers produced in sorption experiments. With their apparently defined structure and ubiquitous nature, these layers could determine the mineralogy and orientation of submarine carbonate cement or could even be a prerequisite to calcification in general.

Description: The release of exchangeable Mg in marine sediments from displacement by ammonium ions was estimated by way of experimentally determining the parameters that govern this ion-exchange equilibrium on solid geochemical phases: smectite, humic acid, illite and opal. We showed that: (a) both the conditional selectivity constant as well as the solid concentration are important parameters in determining the relative contribution of ammonium-exchangeable Mg from smectite, organic matter, illite and opal; and (b) that, except in the cases where opal or organic matter concentrations are very high, the clays are the dominant carrier phases for labile Mg which is exchangeable by ammonium. A model, based on the sum of the contributions from the major geochemical phases present in the sediment reliably predicts the amount of Mg released by exchange with ammonium in marine sediments.

Description: Pore fluids extracted from near-surface sediments of the deformation front along the Oregon subduction zone have, in general, the dissolved nutrient pattern characteristic of bacterial sulfate reduction. However, in certain locations there are peculiar ammonium distributions and anomalously 13C-depleted dissolved ΣCO2. These carbon isotope and nutrient patterns are attributed to the concurrent microbially-mediated oxidation of sedimentary organic matter (POC) and methane (CH4) originating from depth. In contrast to the oxidation of sedimentary organic matter in the sulfate zone, utilization of methane as the carbon source by sulfate-reducing bacteria would generate only half as much total carbon dioxide for each mole of sulfate consumed and would not generate any dissolved ammonium. The isotopically light ΣCO2 released from methane oxidation depletes the total metabolic carbon dioxide pool. Therefore, NH4+, ΣCO2 and δ13C of interstitial carbon dioxide in these pore fluids distintcly reflect the combined contributions of each of the two carbon substrates undergoing mineralization; i.e. methane and sedimentary organic matter. By appropriately partitioning the nutrient and substrate relationships, we calculate that in the area of the marginal ridge of the Oregon subduction zone as much as 30% of the ΣCO2 in pore fluids may result from methane oxidation. The calculation also predicts that the carbon isotope signature of the carbon dioxide derived from methane is between −35‰ and −63‰ PDB. Such an isotopically light gas generated from within the accretionary complex could be the residue of a biogenic methane pool. Fluid advection is required to carry such methane from depth to the present near-surface sediments. This mechanism is consistent with large-scale, tectonically-induced fluid transport envisioned for accreted sediments of the world's convergent plate boundaries.

Description: The deep-sea borehole seal CORK was deployed for the first time on a modern accretionary prism during ODP Leg 146 to the Cascadia Margin. Ten months after the deployment the fluid flow and geochemistry of the borehole fluids was investigated during several dives by DSRV Alvin. The chemical analysis of the borehole fluids revealed methane concentrations of more than 3.5 mM, whereas oxygen and dissolved ions as Cl, NO3, or PO4 are still close to the ambient seawater composition. The exceedingly high methane content measured at the top of the sealed borehole and the observed degassing during the ascent of the submersible indicates that the sampled fluid was initially saturated or close to saturation with respect to CH4. The hydrocarbons are characterized by ratios of 170–200 and δ13C values of − 59.5 to − 62.4%o which indicates a considerable admixture of thermogenic hydrocarbon gases. The occurrence of methane of partly thermogenic origin demonstrates that CH4 enters the sealed borehole in the lower, perforated section (94–178 mbsf) and accumulates at the top of the borehole. This suggests the occurrence of free gas within the encapsulated borehole. Considering the stability field of CH4-hydrates, the formation of these ice-like structures may take place and potentially results in a clogging of the top of the borehole. Such precipitates could result in a decoupling of the top of the borehole from the hydraulic and geochemical regime of the accretionary complex, an important aspect for future plans of CORK deployments.

Description: On active tectonic margins methane-rich pore fluids are expelled during the sediment compaction and dewatering that accompany accretionary wedge development. Once these fluids reach the shallow subsurface they become oxidized and precipitate cold seep authigenic carbonates. Faults or high-porosity stratigraphic horizons can serve as conduits for fluid flow, which can be derived from deep within the wedge and/or, if at seafloor depths greater than ∼300 m, from the shallow source of methane and water contained in subsurface and surface gas hydrates. The distribution of fluid expulsion sites can be mapped regionally using sidescan sonar systems, which record the locations of surface and slightly buried authigenic carbonates due to their impedence contrast with the surrounding hemipelagic sediment. Hydrate Ridge lies within the gas hydrate stability field offshore central Oregon and during the last 15 years several studies have documented gas hydrate and cold seep carbonate occurrence in the region. In 1999, we collected deep-towed SeaMARC 30 sidescan sonar imagery across the Hydrate Ridge region to determine the spatial distribution of cold seep carbonates and their relationship to subsurface structure and the underlying gas hydrate system. High backscatter on the imagery is divided into three categories, (I) circular to blotchy with apparent surface roughness, (II) circular to blotchy with no apparent surface roughness, and (III) streaky to continuous with variable surface roughness. We interpret the distribution of high backscatter, as well as the locations of mud volcanoes and pockmarks, to indicate variations in the intensity and activity of fluid flow across the Hydrate Ridge region. Seafloor observations and sampling verify the acoustic signals across the survey area and aid in this interpretation. Subsurface structural mapping and swath bathymetry suggest the fluid venting is focused at the crests of anticlinal structures like Hydrate Ridge and the uplifts along the Daisy Bank fault zone. Geochemical parameters link authigenic carbonates on Hydrate Ridge to the underlying gas hydrate system and suggest that some of the carbonates have formed in equilibrium with fluids derived directly from the destabilization of gas hydrate. This suggests carbonates are formed not only from the methane in ascending fluids from depth, but also from the shallow source of methane released during the dissociation of gas hydrate. The decreased occurrence of high-backscatter patches and the dramatic reduction in pockmark fields, imaged on the eastern part of the survey, suggest gas hydrate near its upper stability limit may be easily destabilized and thus, responsible for these seafloor features. High backscatter along the left-lateral Daisy Bank fault suggests a long history of deep-seated fluid venting, probably unrelated to destabilized gas hydrate in the subsurface.

Description: Four mud extrusions were investigated along the erosive subduction zone off Costa Rica. Active fluid seepage from these structures is indicated by chemosynthetic communities, authigenic carbonates and methane plumes in the water column. We estimate the methane output from the individual mud extrusions using two independent approaches. The first is based on the amount of CH4 that becomes anaerobically oxidized in the sediment beneath areas covered by chemosynthetic communities, which ranges from 104 to 105 mol yr− 1. The remaining portion of CH4, which is released into the ocean, has been estimated to be 102–104 mol yr− 1 per mud extrusion. The second approach estimates the amount of CH4 discharging into the water column based on measurements of the near-bottom methane distribution and current velocities. This approach yields estimates between 104–105 mol yr−1. The discrepancy of the amount of CH4 emitted into the bottom water derived from the two approaches hints to methane seepage that cannot be accounted for by faunal growth, e.g. focused fluid emission through channels in sediments and fractures in carbonates. Extrapolated over the 48 mud extrusions discovered off Costa Rica, we estimate a CH4 output of 20·106 mol yr− 1 from mud extrusions along this 350 km long section of the continental margin. These estimates of methane emissions at an erosional continental margin are considerably lower than those reported from mud extrusion at accretionary and passive margins. Almost half of the continental margins are described as non-accretionary. Assuming that the moderate emission of methane at the mud extrusions off Costa Rica are typical for this kind of setting, then global estimates of methane emissions from submarine mud extrusions, which are based on data of mud extrusions located at accretionary and passive continental margins, appear to be significantly too high.