Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

Grain-size analysis and geochemistry of sediment core GeoB13602-1

Grain-size, terrigenous element and rock magnetic remanence data of Quaternary marine sediments retrieved at the NW African continental margin off Gambia (gravity core GeoB 13602-1, 13°32.71' N, 17°50.96'W) were jointly analyzed by end-member (EM) unmixing methods to distinguish and budget past terrigenous fluxes. We compare and cross-validate the identified single-parameter EM systems and develop a numerical strategy to calculate associated multi-parameter EM properties. One aeolian and two fluvial EMs were found. The aeolian EM is much coarser than the fluvial EMs and is associated with a lower goethite/hematite ratio, a higher relative concentration of magnetite and lower Al/Si and Fe/K ratios. Accumulation rates and grain sizes of the fluvial sediment appear to be primarily constrained by shore distance (i.e., sea-level fluctuations) and to a lesser extent by changes in hinterland precipitation. High dust fluxes occurred during the Last Glacial Maximum (LGM) and during Heinrich Stadials (HS) while the fluvial input remained unchanged. Our approach reveals that the LGM dust fluxes were ~7 times higher than today's. However, by far the highest dust accumulation occurred during HS 1 (~300 g m**-2 yr** -1), when dust fluxes were ~80 fold higher than today. Such numbers have not yet been reported for NW Africa, and emphasize strikingly different environmental conditions during HSs. They suggest that deflation rate and areal extent of HSs dust sources were much larger due to retreating vegetation covers. Beyond its regional and temporal scope, this study develops new, in principle, generally applicable strategies for multi-method end-member interpretation, validation and flux budgeting calibration.

Chemical composition of clay minerals from ODP Leg 168 sites

The exchangeable cation compositions of organic-poor terrigenous sediments containing smectite as primary ion exchanger from a series of holes along ODP Leg 168 transect on the eastern flank of the Juan de Fuca Ridge have been examined as a function of distance from the ridge axis and burial depth. The total cation exchange capacity (CEC) values of the sediments ranged from 2 to 59 meq/100 g, increasing with increases in the wt.% smectite. At the seafloor, the exchangeable cation compositions involving Na, K, Mg, and Ca, expressed in terms of equivalent fraction, are nearly constant regardless of the different transect sites: XNa = 0.21 ± 0.04, XK = 0.08 ± 0.01, XMg = 0.33 ± 0.09, and XCa = 0.38 ± 0.09. The calculated selectivity coefficients of the corresponding quaternary exchange reactions, calculated using porewater data, are in log units -5.45 ± 0.39 for Na, 1.97 ± 0.49 for K, 0.42 ± 0.41 for Mg, and 3.06 ± 0.69 for Ca. The exchangeable cation compositions below the seafloor change systematically with distance from the ridge crest and burial depth, conforming to the trends of the same cations in the porewaters. The selectivities for Na and Mg are roughly constant at temperatures from 2 to 66°C, indicating that the equivalent fractions of these two cations are independent of sediment alteration taking place on the ridge flank. Unlike Na and Mg, the temperature influence is significant for K and Ca, with Ca-selectivity decreases being coupled with increases in K-selectivity. Although potentially related to diagenetic and/or hydrothermal mineral precipitation or recrystallization, no evidence of such alteration was detected by XRD and TEM. In sites where upwelling of hydrothermal fluids from basement is occurring, the K-selectivity of the sediment is appreciably higher than at the other sites and corresponds to the formation of (Fe, Mg) rich smectite and zeolites. Our study indicates that local increases in K-selectivity at hydrothermal sites are caused by the formation of these authigenic minerals.

Mineralogy of southern Kerguelen Plateau sediments

Kaolinite, goethite, minor hematite, and gibbsite were found in fluvial upper Lower Cretaceous basal sediment from the Southern Kerguelen Plateau, Sites 748 and 750, 55°S latitude. This mineral assemblage, derived from the weathering of basalt, indicates near-tropical weathering conditions with high orographic rainfall, at least 100 cm per year. The climate deteriorated by the Turonian or Coniacian, as indicated by the decline in kaolinite content of this sediment. The Upper Cretaceous sediment at Site 748 consists of 200 m of millimeter-laminated, sparsely fossiliferous, wood-bearing glauconitic siltstone and clay stone with siderite concretions deposited on a shelf below wave base. Some graded and cross beds indicate that storms swept over the shelf and reworked the sediment. Overlying this unit is 300 m of intermittently partly silicified, bryozoan-inoceramid-echinoderm-rich glauconitic packstones, grainstones, and wackestones. The dominant clay mineral in both units is identical to the mineral composition of the glauconite pellets: randomly interstratified smectite-mica. The clay fraction has a higher percent of expandable layers than the mineral of the glauconite pellets, and the clay of the underlying subunit has a higher percentage of expandable layers than the clay of the carbonate subunit. Potassium levels mirror these mineral variations, with higher K levels in minerals that have a lower percentage of expandable layers. The decrease in expandability of the mineral in the upper subunit is attributed to diagenesis, the result of higher porosity.

Geochemistry of vein rocks of ODP Hole 118-735B

Rock samples from Hole 735B, Southwest Indian Ridge, were examined to determine the principal vein-related types of alteration that occurred, the nature of fluids that were present, and the temperatures and pressures of these fluids. Samples studied included veined metagabbro, veined mylonitic metagabbro, felsic trondhjemite, and late-stage leucocratic diopside-bearing veins. The methods used were standard petrographic analysis, mineral chemical analysis by electron microprobe, fluid inclusion petrography and analysis by heating/freezing techniques and laser Raman microspectroscopy, and oxygen isotopic analyses of mineral separates. Alteration in lithologic Units I and II (above the level of Core 118-735B-3OR; approximately 140 meters below the seafloor) is dominated by hydration by seawater-derived fluids at high temperature, up to about 700°C, and low water/rock ratio, during and immediately after pervasive ductile deformation. Below Core 118-735B-30R, pervasive deformation is less common, and brittle veining and brecciation are the major alteration styles. Leucocratic centimeter-scale veins, often containing diopside and plagioclase, were produced by interaction of hot (about 500°C) seawater-derived fluid and gabbro. The water/rock ratio was locally high at the veins and breccia zones, but the integrated water/rock ratio for the lower part of the hole is probably low. Accessory hydrous magmatic or deuteric phases formed from magmatic volatiles in some gabbro and in trondhjemite. Most subsequent alteration was affected by fluids that were seawater-derived, based on isotopic and chemical analyses of minerals and analyses of fluid inclusions. Many early-generation fluid inclusions, associated with high-temperature veining, contain appreciable methane as well as saline water. The source of methane is unclear, but it may have formed as seawater was reduced during low water/rock interaction with ultramafic upper mantle or ultramafic and mafic layer 3. Temperatures of alteration were calculated on the basis of coexisting mineral chemistry and isotopic values. Hydrothermal metamorphism commenced at about 720°C and continued to about 550°C. Leucocratic veining took place at about 500°C. Alteration within brecciated horizons was also at about 500° to less than 400°C, and the trondhjemite was altered at about 550° to below 490°C. Pressures calculated from a diopside-bearing vein, based on a combination of fluid inclusion and isotopic analysis, were 90 to 100 MPa. This pressure places the sample, from Core 118-735B-70R in Unit V, at about 2 km below the seafloor.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

Biogeochemistry of the Eastern Weddell Gyre

The Southern Ocean (SO) plays a key role in modulating atmospheric CO2 via physical and biological processes. However, over much of the SO, biological activity is iron-limited. New in situ data from the Antarctic zone south of Africa in a region centered at -20°E - 25°E reveal a previously overlooked region of high primary production, comparable in size to the northwest African upwelling region. Here, sea ice together with enclosed icebergs is channeled by prevailing winds to the eastern boundary of the Weddell Gyre, where a sharp transition to warmer waters causes melting. This cumulative melting provides a steady source of iron, fuelling an intense phytoplankton bloom that is not fully captured by monthly satellite production estimates. These findings imply that future changes in sea-ice cover and dynamics could have a significant effect on carbon sequestration in the SO.

EPOCA/EUR-OCEANS data compilation on the effects of ocean acidification, 2011

The uptake of anthropogenic CO2 by the oceans has led to a rise in the oceanic partial pressure of CO2, and to a decrease in pH and carbonate ion concentration. This modification of the marine carbonate system is referred to as ocean acidification. Numerous papers report the effects of ocean acidification on marine organisms and communities but few have provided details concerning full carbonate chemistry and complementary observations. Additionally, carbonate system variables are often reported in different units, calculated using different sets of dissociation constants and on different pH scales. Hence the direct comparison of experimental results has been problematic and often misleading. The need was identified to (1) gather data on carbonate chemistry, biological and biogeochemical properties, and other ancillary data from published experimental data, (2) transform the information into common framework, and (3) make data freely available. The present paper is the outcome of an effort to integrate ocean carbonate chemistry data from the literature which has been supported by the European Network of Excellence for Ocean Ecosystems Analysis (EUR-OCEANS) and the European Project on Ocean Acidification (EPOCA). A total of 185 papers were identified, 100 contained enough information to readily compute carbonate chemistry variables, and 81 data sets were archived at PANGAEA - The Publishing Network for Geoscientific & Environmental Data. This data compilation is regularly updated as an ongoing mission of EPOCA.

Molecular fingerprinting and amplicon sequencing of the bacterial biofilm on settlement tiles deployed along natural pH gradients in Papua New Guinea

Bacterial biofilms provide cues for the settlement of marine invertebrates such as coral larvae, and are therefore important for the resilience and recovery of coral reefs. This study aimed to better understand how ocean acidification may affect the community composition and diversity of bacterial biofilms on surfaces under naturally reduced pH conditions. Settlement tiles were deployed at coral reefs in Papua New Guinea along pH gradients created by two CO2 seeps, and upper and lower tiles surfaces were sampled 5 and 13 months after deployment. Automated Ribosomal Intergenic Spacer Analysis were used to characterize more than 200 separate bacterial communities, complemented by amplicon sequencing of the bacterial 16S rRNA gene of 16 samples. The bacterial biofilm consisted predominantly of Alpha-, Gamma- and Deltaproteobacteria, as well as Cyanobacteria, Flavobacteriia and Cytophaga, whereas putative settlement-inducing taxa only accounted for a small fraction of the community. Bacterial biofilm composition was heterogeneous with approximately 25% shared operational taxonomic units between samples. Among the observed environmental parameters, pH only had a weak effect on community composition (R² ~ 1%) and did not affect community richness and evenness. In contrast, there were strong differences between upper and lower surfaces (contrasting in light exposure and grazing intensity). There also appeared to be a strong interaction between bacterial biofilm composition and the macroscopic components of the tile community. Our results suggest that on mature settlement surfaces in situ, pH does not have a strong impact on the composition of bacterial biofilms. Other abiotic and biotic factors such as light exposure and interactions with other organisms may be more important in shaping bacterial biofilms than changes in seawater pH.