ALBERT

Description: In order to develop the potential tool of diatom oxygen isotopes for paleoenvironmental studies we compared oxygen isotopes of natural marine diatoms sampled from ocean surface water, sediment traps and surface sediments with oxygen isotopic fractionations determined for laboratory diatom cultures. Freshly grown natural diatoms (phytoplankton samples and sediment trap material) and cultured diatoms reveal similar oxygen isotope fractionation factors. The fresh diatoms have 3 to 10 parts per thousand lower isotope fractionation factors than fossil (sedimentary) diatoms. A temperature-related oxygen isotope fractionation could not be established for the laboratory cultures (and the natural phytoplankton samples), and there is evidence that diatom growth rate until reaching the stationary growth state also controls the measured silica-water oxygen isotope fractionation factor. It is possible, however, that slow diatom growth in sea surface water may well lead to a temperature-dependent silica-water oxygen isotope fractionation which is the prerequisite for a use of diatom oxygen isotopes in palco-surface water studies. FTIR-spectroscopic analyses of various diatomaceous materials revealed that the ratio of integrated peak intensities for Si-O-Si/Si-OH correlates with the 3 to 10 parts per thousand delta O-18(silica) increase from fresh to fossil diatoms. Open-system (flow-through) silica dissolution experiments suggest that the diatom frustules are isotopically homogenous and that the increase in O-18 is therefore not due to dissolution of isotopically light surficial Si-OH groups. It is concluded that slow internal condensation reactions during silica maturation in surface sediments cause both an increase in the intensity ratio of Si-O-Si/Si-OH and the O-18 content of framework oxygen. These findings also indicate that the oxygen isotope compositions of marine sediment diatoms do not indicate sea surface water temperature but rather reflect variable O-18 contents of surface sediments. Copyright (C) 2001 Elsevier Science Ltd.

Description: During the expeditions ANT-XV/2 with R/V Polarstern in 1997/98 and NBP 99-04 with R/V IB N.B. Palmer in 1999, the first samples of hydrothermally influenced sediments of Bransfield Strait were obtained at Hook Ridge, a volcanic edifice in the Central Basin of the Strait. The vent sites are characterized by white siliceous crusts on top of the sediment layer and temperatures measured immediately on deck are up to 48.5°C. The shallow depth of these vent sites (1050 m) particularly controls the chemistry of the pore fluids that are enriched in silica and sulfide and show low pH values. Chloride is depleted up to 20% and the calculated hydrothermal endmember concentration is in the range of 1–84 mM. Since other mechanisms for Cl depletion can be ruled out clearly, the composition of this fluid is attributed to phase separation. While the Cl-depleted fluid is emanating at Hook Ridge, a Cl-enriched fluid can be identified in the adjacent King George Basin. Using a p,x diagram the two corresponding endmember concentrations reveal that the phase separation takes place at subcritical conditions (total depth: ∼2500 m), probably along the whole volcanic edifice

Description: A numerical model was applied to investigate and quantify the biogeochemical processes fueled by the expulsion of barium and methane-rich fluids in the sediments of a giant cold-seep area in the Derugin Basin (Sea of Okhotsk). Geochemical profiles of dissolved Ba2+, Sr2+, Ca2+, SO42−, HS−, DIC, I− and of calcium carbonate (CaCO3) were fitted numerically to constrain the transport processes and the kinetics of biogeochemical reactions. The model results indicate that the anaerobic oxidation of methane (AOM) is the major process proceeding at a depth-integrated rate of 4.9 μmol cm−2 a−1, followed by calcium carbonate and strontian barite precipitation/dissolution processes having a total depth-integrated rate of 2.1 μmol cm−2 a−1. At the low seepage rate prevailing at our study site (0.14 cm a−1) all of the rising barium is consumed by precipitation of barite in the sedimentary column and no benthic barium flux is produced. Numerical experiments were run to investigate the response of this diagenetic environment to variations of hydrological and biogeochemical conditions. Our results show that relatively low rates of fluid flow (〈∼5 cm a−1) promote the dispersed precipitation of up to 26 wt% of barite and calcium carbonate throughout the uppermost few meters of the sedimentary column. Distinct and persistent events (several hundreds of years long) of more vigorous fluid flow (from 20–110 cm a−1), instead, result in the formation of barite-carbonate crusts near the sediment surface. Competition between barium and methane for sulfate controls the mineralogy of these sediment precipitates such that at low dissolved methane/barium ratios (〈4–11) barite precipitation dominates, while at higher methane/barium ratios sulfate availability is limited by AOM and calcium carbonate prevails. When seepage rates exceed 110 cm a−1, barite precipitation occurs at the seafloor and is so rapid that barite chimneys form in the water column. In the Derugin Basin, spectacular barite constructions up to 20 m high, which cover an area of roughly 22 km2 and contain in excess of 5 million tons of barite, are built through this process. In these conditions, our model calculates a flux of barium to the water column of at least 20 μmol cm−2 a−1. We estimate that a minimum of 0.44 × 106 mol a−1 are added to the bottom waters of the Derugin Basin by cold seep processes, likely affecting the barium cycle in the Sea of Okhotsk.

Description: Significant sediment–ocean chemical fluxes are produced by the expulsion of sedimentary fluids at continental margins. Although such fluxes could play a role in global geochemical cycles, few quantitative estimates of their global, or even regional, significance exist. We carried out a pore water geochemical study of fluids expelled from the Dvurechenskii mud volcano (DMV) in the Black Sea, with the aim of understanding the role played by mud volcanoes in Black Sea geochemical cycles. The DMV is presently expelling highly saline fluids particularly enriched in geochemically important species such as Li+ (1.5 mM), B (2.17 mM), Ba2+ (0.57 mM), Sr2+ (0.79 mM), I (0.4 mM) and dissolved inorganic nitrogen (DIN) (22 mM). A combination of geochemical indicators shows that this geochemical signature was acquired via organic matter and silicate alteration processes in the subsurface down to 3-km depth and near-surface gas hydrate formation. We used a simple transport model to estimate the benthic fluxes of these solutes at the DMV. Our results show that the DMV is expelling fluids at a rather low seepage rate (8–25 cm year−1) resulting in a total water flux of 9.4×10−5 km3 year−1. This gentle regime of fluid expulsion results in Li+, B, Sr2+, I and DIN fluxes between 3.8×104 and 2.1×106 mol year−1. Surface biogeochemical processes affect the benthic fluxes of Ba2+ such that the deep Ba2+ flux is completely consumed through the precipitation of authigenic barite (BaSO4) in surface sediments. The Black Sea I cycle is likely to be affected by mud volcanism, if the 50 known Black Sea mud volcanoes share the rather sluggish activity of the DMV. Mud volcano fluxes of Li, B, Sr and DIN, instead, are too small to affect Black Sea geochemical cycles. On a global scale, mud volcanism could play a role in the marine cycles of Li, B, Sr, I and DIN if current estimates of mud volcano abundance are correct.

Description: At the summit of Hydrate Ridge (ODP Sites 1249 and 1250), pore fluids are highly enriched in dissolved chloride (up to 1370 mM) in a zone that extends from near the sediment surface (∼1 mbsf) to depths of 25±5 mbsf. Below this depth, brines give way to chloride values approaching seawater concentrations with lower chloride anomalies superimposed on baseline values. We developed a one dimensional, non-steady state, transport reaction model to simulate the observed chloride enrichment at Site 1249. Our model shows that in order to reach the observed high chloride values, methane must be transported in the gas phase from the depth of the BSR to the seafloor. Methane transport exclusively in the dissolved phase is not enough to form methane hydrate at the rates needed to generate the observed chloride enrichment. Methane transport in the gas phase is consistent with geophysical and logging data, estimates of gas pressure beneath the BSR, and observations of bubble plumes at the seafloor. In order to reproduce the observed chloride and gas hydrate distributions, the model requires an enhanced rate of hydrate formation in near surface sediments, which we implement through depth-dependent kinetic constants. We argue that this is justified by changes in geomechanical properties of the sediment. At depths shallower than 25 mbsf the force of crystallization can overcome effective overburden stress, and hydrate growth proceeds by particle displacement, thus minimizing capillary inhibition effects. Our calculations indicate the hydrates in the upper sediments of the ridge summit are probably younger than 1500 years, although the age is difficult to constrain. Independent estimates based on seafloor observations at this site yield gas hydrate formation rates at the ridge crest on the order of 102 mol m−2 year−1. These rates are several orders of magnitude higher than those estimated for Site 997 on the Blake Ridge

Description: An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (∼1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative δ13C values of these carbonates (〉−43.5‰ PDB) indicate methane as major carbon source; δ18O values between 4.04 and 5.88‰ PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to 〉49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO42- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (δ34S: 21.0–38.6‰ CDT; δ18O: 9.0–17.6‰ SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with ‘normal’ seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Description: Uranium (U) concentrations and activity ratios (δ 234U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids ("cold seeps") at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 μg/g) and high δ 234U values (165-317‰) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their 230Th/ 234U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 μg/g) and a mean δ 234U ratio of 166 ± 3‰. Their U isotopes reflect the δ 234U ratios of the bottom water being enriched in 234U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding δ 234U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. 230Th/ 234U ages of chemoherm carbonates range from 7.3 to 267.6 ka. 230Th/ 234U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The δ 18O PDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm δ 18O values from the marine δ 18O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.