Volatile fatty acid cycling in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates were determined by measuring whole sediment VFA concentrations and the corresponding reaction rate constants. The following ranges of VFA concentrations were measured in Cape Lookout Bight, N.C. sediments (μmole·l_s^?1): acetate 54–660, propionate 1–24, butyrate <0.5–22, iso-butyrate <0.5–6. Apparent turnover rates measured over a one-year period ranged from 18–600 μmole·l_s^?1·h^?1 for acetate and 0.7–7 μmole·l_s^?1·h^?1 for the carboxyl carbon of propionate. Methane production was observed only with acetate and only in sulfatedepleted sediments; total acetate turnover attained approximately the same maximum value in both sulfate-reducing and sulfate-depleted sediments.Apparent turnover rates for acetate and propionate appeared to be controlled by similar factors: in sulfate-reducing (surface) sediments the turnover rates were stimulated by autumn storm-mediated deposition/resuspension events; in deeper sulfate-depleted sediments the turnover rates followed changes in the ambient temperature. Changes in VFA poolsizes were proportionally much larger than changes in corresponding rate constants. The ratio of CO₂ to CH₄ produced from acetate vs. depth suggested that non-methanogenic bacteria accounted for 60% of the acetate turnover in sulfate-depleted sediments.VFA concentrations were much lower in N.C. continental slope mud than in Cape Lookout sediments; acetate was the only VFA detectable throughout the top 40 cm of the slope sediments. The estimated production rate of CO₂ from acetate decreased rapidly with depth. The surface rate was approximately 20 times less than that measured at similar temperatures in sulfate-reducing Cape Lookout sediments.     

Anaerobic diagenesis of silica and carbon in continental margin sediments: Discrete zones of TCO2 production

Pore water profiles of dissolved Si, Ca²⁺, SO₄^2-, CH₄, and TCO₂ (Dissolved Inorganic Carbon; DIC) were determined from multicores and gravity cores collected at nine sites off Southern California, the west coast of Mexico, and within the Gulf of California. These sites were located within the eastern North Pacific oxygen minimum zone at depths of 400 to 900 m and in settings where bottom water oxygen concentrations were <3 μM and sediments were laminated. Pore water profiles were defined at a resolution of millimeters (whole core squeezing), centimeters (sectioning and squeezing) and meters (gravity core sectioning and squeezing), and diffusive fluxes were calculated for different zones within the sediment column. The flux of dissolved silica across the sediment-water interface (SWI) ranged from 0.3 to 3.4 mmol Si m^-2d^-1, and TCO₂ fluxes ranged from 0.8 to 4.6 mmol C m^-2d^-1. A positive correlation (r = 0.74) existed between these fluxes, yet these two constituents exhibited significantly different diagenetic behavior downcore; dissolved Si generally reached a constant concentration (between 450 and 900 μM) in the upper few cm, whereas TCO₂ concentrations increased monotonically with depth.Methane was detected at micromolar levels in sediment intervals between 0 and 60 cm and at five sites, increased to millimolar levels at depths of 80 to 170 cm. At the horizon marking the appearance of millimolar levels of methane, there was a distinct change in slope of the sulfate and TCO₂ gradients. A flux budget for this horizon was determined by using linear fits to pore water profiles; these budgets indicate that the upward TCO₂ flux away from this horizon is 40 to 50% greater than the downward sulfate flux to this horizon. Given that the TCO₂ flux to this horizon from below was quite small, this imbalance suggests that anaerobic oxidation of methane by sulfate is not the only process producing TCO₂ within this horizon. A budget for TCO₂ at this horizon is balanced when 40 to 80% of the sulfate flux is attributed to organic carbon remineralization. Of the DIC that diffuses across the SWI, 20 to 40% is generated by reactions occurring within or below this deep reaction horizon.     

Biogeochemical cycling in an organic-rich coastal marine basin—I. Methane sediment-water exchange processes

Methane produced in anoxic organic-rich sediments of Cape Lookout Bight, North Carolina, enters the water column via two seasonally dependent mechanisms: diffusion and bubble ebullition. Diffusive transport measured in situ with benthic chambers averages 49 and 163 μmol · m ^?2 · hr ^?1 during November–May and June–October respectively. High summer sediment methane production causes saturation concentrations and formation of bubbles near the sediment-water interface. Subsequent bubble ebullition is triggered by low-tide hydrostatic pressure release. June–October sediment-water gas fluxes at the surface average 411 ml (377 ml STP: 16.8 mmol) · m^?2 per low tide. Bubbling maintains open bubble tubes which apparently enhance diffusive transport. When tubes are present, apparent sediment diffusivities are 1.2–3.1-fold higher than theoretical molecular values reaching a peak value of 5.2 × 10^?5 cm² · sec^?1. Dissolution of 15% of the rising bubble flux containing 86% methane supplies 170μmol · m^?2 · hr^?1 of methane to the bight water column during summer months; the remainder is lost to the troposphere. Bottom water methane concentration increases observed during bubbling can be predicted using a 5–15 μm stagnant boundary layer dissolution model. Advective transport to surrounding waters is the major dissolved methane sink: aerobic oxidation and diffusive atmospheric evasion losses are minor within the bight.     

Spatial and temporal distribution of methane in an extensive shallow estuary, South India

Sedimentary methane (CH₄) fluxes and oxidation rates were determined over the wet and dry seasons (four measurement campaigns) in Pulicat lake, an extensive shallow estuary in south India. Dissolved CH₄ concentrations were measured at 52 locations in December 2000. The annual mean net CH₄ flux from Pulicat lake sediments was 3.7 × 10⁹ g yr^-1 based on static chamber measurements. A further 1.7 × 10⁹g yr_-1 was estimated to be oxidized at the sediment-water interface. The mean dissolved concentration of CH₄ was 242nmol |^-1 (ranging between 94 and 501 nmol |^-1) and the spatial distribution could be explained by tidal dynamics and freshwater input. Sea-air exchange estimates using models, account only for ∼13% (0.5 × 10⁹ g yr-1) of the total CH₄ produced in sediments, whereas ebullition appeared to be the major route for loss to the atmosphere (∼ 63% of the net sediment flux). We estimated the total atmospheric source of CH₄ from Pulicat lake to be 0.5 to 4.0 × 10⁹g yr^-1.     

Biogeochemical cycling in an organic rich coastal marine basin—II. Nutrient sediment-water exchange processes

The release of remineralized N and P from the organic-rich anoxic sediments of Cape Lookout Bight is controlled by processes occurring within the sediment column and at the sediment-water interface. The relatively rapid rates of temperature dependent microbial degradation of organic matter support seasonally varying nutrient fluxes ranging from 20 to 1200 μmol·m^?2·hr^?1 for dissolved ammonium and from ? 20 to 120 μmol·m^?2·hr^?1 for total dissolved phosphate (measured in situ over the period October, 1976 to October, 1978). Molecular diffusion along steep vertical pore water concentration gradients measured simultaneously cannot explain the high fluxes observed during warmer months. Gradients for ammonium and phosphate ranged from 0.33 to 1.10 and from 0 to 0.29 μmol·cm^?3_pw·cm^?1_s respectively. These high summertime fluxes appear to result from increased sediment-water transport associated with bubble tubes created and maintained by low-tide methane gas bubble ebullition. When these tubes are present, apparent bulk sediment diffusivities calculated from concurrent studies of methane and radon-222 sediment-water exchange are 1.0–3.1 times greater than molecular diffusivities. Nutrient fluxes calculated via Fick's first law taking into account this enhanced transport and the differential diffusive mobilities of dissolved ammonium, phosphate and phosphate ion pairs indicate that removal by aerobic adsorption and/or biological uptake at the sediment-water interface plays an important role in controlling nutrient exchange in these sediments.     

Rates of iodine remineralization in terrigenous near-shore sediments

Much of the sedimentary geochemistry of iodine has been surmised from analyses of solid phase distributions without direct documentation of reactions or reaction rates. It is shown here that the anoxic production rate of dissolved I in nearshore terrigenous sediments decreases rapidly below the sediment-water interface and is strongly temperature controlled. An apparent activation energy of ~19.3 Kcal/mole comparable to that found for other microbially mediated reactions, describes the temperature dependence of release. Production of dissolved iodide is zeroth order with respect to natural ranges of pore water concentrations and apparently first-order with respect to a reactive I component in the solid phase. First order reaction coefficients in sediments from Mud Bay, South Carolina and Long Island Sound, Connecticut, U.S.A., are strongly depth dependent, varying from ~6.9/yr in the top few centimeters to an average of ~0.011/yr over the upper 70 cm. About 90% of the dissolved I flux comes from the top 10 cm with estimated values of ~ 15 and 29 μmoles/m²/day at 22–23°C in Mud Bay and Long Island Sound, respectively. The I/C net release ratio of decomposing material changes rapidly below the sediment surface. When temperature corrections are made, I remineralization rates from nearshore sediments below the bioturbated zone appear to be similar to those observed in deep water sediments underlying oxygenated waters.     

Methane production in Mississippi River deltaic plain peat

Seasonal methane production in a coastal peat deposit was studied. Dissolved methane content in interstitial water increased with increasing depth. Methane production rate was related to temperature in the 0–40 cm depth, but was relatively constant at depths below 40 cm. Maximal methane content was found in spring and lowest content in November to January. Production rates were pH dependent, with an optimum rate of methanogenesis at pH 7.7. The accumulation of metabolic end products produced within the peat-water matrix appear to be important in limiting methanogenesis in wetland ecosystems. The reserve of methane in the interstitial water of the brackish marsh was estimated to be 15.8 g CH₄ m⁻² or 221 CH₄ per m⁻². Results suggest that the vast peat deposits in the Mississippi deltaic plain could possibly be a potential source of renewable energy if in situ method for removal of the produced methane could be developed.     

Controls on the stable carbon isotopic composition of biogenic methane produced in a tidal freshwater estaurine sediment

The δ¹³C value of methane in sediments from a tidal freshwater site in the White Oak River Estuary, North Carolina, exhibited a relatively small, but consistent, seasonal variation (∼3‰) with isotopically heavier values occurring during the warmer months (−66.1‰ summer, −69.2‰ winter). These isotopic shifts could have resulted from changes in: (1) isotopic compositions of precursor molecules; (2) kinetic isotope effects associated with methane production; or (3) pathways of methane production. Methane production rate and isotopic data from sediment incubation experiments and field measurements were used to determine the relative contributions of these factors to the observed seasonal variations. Although changes in δ¹³C values of biogenic methane are typically thought to result from changes in pathways of methane production, this study showed that a significant amount (36 ± 22%) of the seasonal variations between the δ¹³C value of methane produced in sediment incubation experiments could be attributed to changes in the δ¹³C value of the ΣCO₂ pool. This was due to increased methane production rates and removal of ¹²CO₂ with increasing temperature, a prevalent feature of methanogenic systems that may account for some of the frequently observed ¹³C enrichment in methane during warmer months. Combining the change in the δ¹³C value of the ΣCO₂ pool with temperature-controlled changes in fractionation (α) resulting from kinetic isotope effects accounted for (53 ± 22%) of the ¹³C enrichment observed during summer sediment incubation experiments. Although large pathway changes were not observed in sediment incubation experiments, the remaining differences in δ¹³C values could have resulted from smaller, undetectable changes in the percentage of methane production from acetate (∼14%) and/or a shift in the δ¹³C values of methane produced from acetate (∼4‰).     

Sources and flux of natural gases from Mono Lake,California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH₄ day⁻¹, and estimate total lakewide annual seep flux to be 2.1 × 10⁶ moles CH₄. Geochemical parameters (δ¹³CH₄,δDCH₄,CH₄/[C₂H₆+ C₃H₈]) andδ¹⁴CH₄measurements revealed that most of the seeps originate from a paleo-biogenic (δ¹³CH₄ = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2–3 mM at 50 cm; δ₁₃CH₄ = about −85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 μM in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1–1.3μM) were supersaturated with respect to the atmosphere. The δ¹³CH₄ (range = −21.8 to −71.8%.) of this unoxidized residual methane was enriched in ¹³C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 × 10⁷ moles yr⁻¹. A fourth, but minor source of methane (δ¹³CH₄ = −55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone.     

Anaerobic Carbon Mineralisation Through Sulphate Reduction in the Inner Shelf Sediments of Eastern Arabian Sea

Monsoon-induced coastal upwelling, land run-off, benthic and atmospheric inputs make the western Indian shelf waters biologically productive that is expected to lead to high rates of mineralisation of organic matter (OM) in the sediments. Dissimilatory sulphate reduction (SR) is a major pathway of OM mineralisation in near-shore marine sediments owing to depletion of other energetically more profitable electron acceptors (O₂, NO₃ ^?, Mn and Fe oxides) within few millimetres of the sediment-water interface. We carried out first ever study to quantify SR rates in the inner shelf sediments off Goa (central west coast of India) using the ³⁵S radiotracer technique. The highest rates were recorded in the upper 10 cm of the sediment cores and decreased gradually thereafter below detection. Despite significant SR activity in the upper ～12 to 21 cm at most of the sites, pore water sulphate concentrations generally did not show much variation with depth. The depth integrated SR rate (0.066–0.46 mol m^?2 year^?1) decreased with increasing water depth. Free sulphide was present in low concentrations (0–3 μM) in pore waters at shallow stations (depth <30 m). However, high build-up of sulphide (100–600 μM) in pore waters was observed at two deeper stations (depths 39 and 48 m), 7–11 cm below the sediment-water interface. The total iron content of the sediment decreased from ～7 to 5 % from the shallowest to the deepest station. The high pyrite content indicates that the shelf sediments act as a sink for sulphide accounting for the low free sulphide levels in pore water. In the moderately organic rich (2–3.5 %) sediments off Goa, the measured SR rates are much lower than those reported from other upwelling areas, especially off Namibia and Peru. The amount of organic carbon remineralised via sulphate reduction was ～0.52 mol m^?2 year^?1. With an estimated average organic carbon accumulation rate of ～5.6 (±0.5) mol m^?2 year^?1, it appears that the bulk of organic matter gets preserved in sediments in the study region.     

Acyclic archaebacterial ether lipids in swamp sediments

Acyclic phytanyl diether glycerol and biphytanyl ether lipids have been quantified in two modern swamp sediment cores in concentrations ranging up to 360 μg/ml porewater. Methanogenic bacteria are the only known source organisms which can inhabit the swamp sediments. Variations in relative abundance between these lipids may reflect taxonomic changes in methanogen populations or the stage of growth. Maxima in methanogen lipid concentrations coincide with local maxima of ¹³C of organic matter, possibly the result of a pool effect on CO₂ or acetate. Methane production estimates calculated from lipid concentrations in swamp sediments range from 0.1 to 1.3 mmol cm⁻² yr⁻¹, values which are consistent with published methane fluxes.     

The oxidation state of manganese in surface sediments of the deep sea

Iodometric titration of deep sea sediment from cores at MANOP sites M and H indicate a particulate Mn oxidation state between 3.3 and 3.9 in the top 5 cm. Results from site H show a minimum in the Mn oxidation state at 1.5 cm depth indicating Mn reduction is occurring above the zone of pore water Mn oxidation. Using a simple box model, the rate of reduction is calculated to be 19 mg/cm² kyr ? 77 mg/cm² kyr, at least 5 times the flux of Mn to nodules in this region. Although no Mn oxidation state minimum is observed in site M sediments, oxic reduction is inferred from a particulate mass balance, indicating that a large fraction of the Mn rain to this site is not preserved in the sediments and must be remobilized. We suggest that the process of reduction in oxic or suboxic environments near the sediment-water interface may be an important mechanism controlling the concentration of Mn in sediments and provides a mechanism for supplying diagenetic Mn to the nodules at site H.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

The influence of tidal action on porewater nitrate concentration and dynamics in intertidal sediments of the Sado estuary

The change in porewater nitrate (NO₂ ^? + NO₃ ^?) concentrations during exposure of intertidal sediment was studied at a fixed location in the Sado estuary, southwest Portugal, in November 1994. In order to follow nitrate concentration and dynamics from pre-ebb to post flood, during the day, high vertical resolution profiles (0.2 cm) were studied. As a complement, in February 1995, potential nitrification rates in the sediment were measured by laboratory incubations, with high vertical resolution (0.2 cm) up to 3 cm depth. Oxygen penetration was measured with polarographic mini-electrodes. The sediment’s texture as well as the organic matter composition in carbon and nitrogen were studied in deeper (30 cm) cores. In February 1993,²¹⁰Pb activity depth profiles were measured in a core sampled at the beginning of exposure, in order to evaluate the possibility of nonlocal particle exchange. C:N ratios and²¹⁰Pb activity profiles show evidence of nonlocal exchange of solid phase particles between the surface and deeper sediment, most likely due to macrofaunal activity. As a consequence, fresh organic matter is brought from the surface to 7–9 cm depth, causing enhancement of nutrient concentrations. Results of this study suggest nitrate dynamics in intertidal sediments of the Sado estuary are strongly influenced by tidal action. Periodic submersion and exposure allow for the diversification of pathways of oxygen supply to the sediment. Tidal stress at the sediment-water interface during the arrival (flooding) and departure (exposure) of the tidal front at the site has an important bearing on the effective depth of the nitrification zone. A denitrification rate of 2.16 μmol N dm^?5 h^?1 was measured directly from the nitrate inventory in the 1.5–6 cm depth layer. The schematic model of N cycling in these sediments suggests that 20% of the N pool is denitrified during exposure, and that this process is limited by O₂ availability for nitrification.     

Sediment community metabolism associated with continental shelf hypoxia, Northern Gulf of Mexico

Net fluxes of respiratory metabolites (O₂, dissolved inorganic carbon (DIC), NH₄ ⁺, NO₃ ^?, and NO₂ ^?) across the sediment-water interface were measured using in-situ benthic incubation chambers in the area of intermittent seasonal hypoxia associated with the Mississippi River plume. Sulfate reduction was measured in sediments incubated with trace levels of³⁵S-labeled sulfate. Heterotrophic remineralization, measured as nutrient regeneration, sediment community oxygen consumption (SOC), sulfate reduction, or DIC production, varied positively as a function of temperature. SOC was inversely related to oxygen concentration of the bottom water. The DIC fluxes were more than 2 times higher than SOC alone, under hypoxic conditions, suggesting that oxygen uptake alone cannot be used to estimate total community remineralization under conditions of low oxygen concentration in the water column. A carbon budget is constructed that compares sources, stocks, transformations, and sinks of carbon in the top meter of sediment. A comparison of remineralization processes within the sediments implicates sulfate reduction as most important, followed by aerobic respiration and denitrification. Bacteria accounted for more than 90% of the total community biomass, compared to the metazoan invertebrates, due presumably to hypoxic stress.     

Biogeochemical cycling in an organic-rich coastal marine basin—3. Dissolved gas transport in methane-saturated sediments

The transport of dissolved gases in the anoxic sediments of Cape Lookout Bight, North Carolina, is controlled by diffusion and bubble ebullition and exhibits a distinct seasonal cycle. Detailed seasonal profiles of CH₄, N₂ and ²²²Rn and direct gas flux measurements indicate that ebullition dominates the flux of all dissolved gases across the sediment-water interface during summer months, and is of major importance on an annual basis. Transport within the upper 6–8 cm of sediment appears to be controlled by molecular diffusion of gases. Transport at greater depths is controlled by diffusion in winter and ebullition in summer. Rn-222 profiles were used to estimate the rate of stripping of dissolved gases within the CH₄ production zone (10–30 cm); rates averaged 3–5 percent per day and agreed with estimates derived from N₂ profiles. As a result of summer ebullition, the sediments of the bight are never at saturation with respect to the major gases present in seawater. Evidence from other sites suggests that ebullition may be an important transport process in many coastal sediments, and may provide mechanism for the transport of volatile reduced compounds between anoxic sediments and the atmosphere. ²²²Rn is a useful tracer for quantifying this transport.     

Fluid flow, methane fluxes, carbonate precipitation and biogeochemical turnover in gas hydrate-bearing sediments at Hydrate Ridge, Cascadia Margin: numerical modeling and mass balances

A numerical model was applied to investigate and to quantify biogeochemical processes and methane turnover in gas hydrate-bearing surface sediments from a cold vent site situated at Hydrate Ridge, an accretionary structure located in the Cascadia Margin subduction zone. Steady state simulations were carried out to obtain a comprehensive overview on the activity in these sediments which are covered with bacterial mats and are affected by strong fluid flow from below. The model results underline the dominance of advective fluid flow that forces a large inflow of methane from below (869 μmol cm⁻² a⁻¹) inducing high oxidation rates in the surface layers. Anaerobic methane oxidation is the major process, proceeding at a depth-integrated rate of 870 μmol cm⁻² a⁻¹. A significant fraction (14%) of bicarbonate produced by anaerobic methane oxidation is removed from the fluids by precipitation of authigenic aragonite and calcite. The total rate of carbonate precipitation (120 μmol cm⁻² a⁻¹) allows for the build-up of a massive carbonate layer with a thickness of 1 m over a period of 20,000 years. Aragonite is the major carbonate mineral formed by anaerobic methane oxidation if the flow velocity of methane-charge fluids is high enough (≥10 cm a⁻¹) to maintain super-saturation with respect to this highly soluble carbonate phase. It precipitates much faster within the studied surface sediments than previously observed in abiotic laboratory experiments, suggesting microbial catalysis. The investigated station is characterized by high carbon and oxygen turnover rates (≈1000 μmol cm⁻² a⁻¹) that are well beyond the rates observed at other continental slope sites not affected by fluid venting. This underlines the strong impact of fluid venting on the benthic system, even though the flow velocity of 10 cm a⁻¹ derived by the model is relative low compared to fluid flow rates found at other cold vent sites. Non-steady state simulations using measured fluid flow velocities as forcing demonstrate a rapid respond of the sediments within a few days to changes in advective flow. Moreover, they reveal that efficient methane oxidation in these sediments prevents methane outflow into the bottom water over a wide range of fluid flow velocities (<80 cm a⁻¹). Only at flow rates exceeding approximately 100 cm a⁻¹, does dissolved methane break through the sediment surface to induce large fluxes of up to 5000 μmol CH₄ cm² a⁻¹ into the overlying bottom water.     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

The early diagenesis of aliphatic hydrocarbons and organic matter in sedimentary particulates from Dabob Bay,Washington

Aliphatic hydrocarbon compositions were quantitatively characterized in plankton, sediment trap-collected particulate materials and sediments from Dabob Bay using high resolution glass capillary gas chromatography. The average net accumulation of individual hydrocarbons measured in a 1-yr series of sediment traps was compared with the net accumulation of corresponding compounds measured in three depth intervals of ²¹⁰Pb-dated bottom sediments. Systematic and rapid decreases in the net accumulation of individual hydrocarbons were observed from the sediment traps to the sediments. Most pronounced decreases were measured for planktonically derived hydrocarbon constituents (e.g. pristane and two unsaturated compounds) which are rapidly remineralized at or near the sediment-water interface. Consequently, the amount of each compound measured in deposited sediments is not necessarily a quantitative indication of its initial flux to the sediments. The n-alkanes (C_25,27,29,31). characteristic of terrestrial plant waxes, are the predominant hydrocarbons measured by 4–6 cm depth in these sediments and show reasonably constant net accumulation below this interval.Significant diagenetic alteration of the bulk organic matter contained in the average sediment trap particulate material is also noted through comparison with bottom sediments on the basis of organic C/N and δ¹³C measurements. Organic matter elementally similar to marine plankton is preferentially remineralized upon deposition of the sedimentary particulates. The residual organic matter remaining and buried in the bottom sediments closely resembles terrestrial organic matter.     

Recycling of Organic Matter in the Sediments of Santa Monica Basin,California Borderland

Geochemical and isotopic data for the uppermost 1.2 m of the sediments of the central Santa Monica Basin plain were examined to better understand organic matter deposition and recycling at this site. Isotopic signatures (Δ¹⁴C and δ¹³C) of methane (CH₄) and dissolved inorganic carbon (DIC) indicate the occurrence of anaerobic oxidation of CH₄ that is fueled by CH₄ supplied from a relict reservoir that is decoupled from local organic carbon (C_org) degradation and methanogenesis. This finding was corroborated by a flux budget of pore-water solutes across the basal horizon of the profile. Together these results provide a plausible explanation for the anomalously low ratio between alkalinity production and sulfate consumption reported for these sediments over two decades ago. Shifts in Δ¹⁴C and δ¹³C signatures of C_org have previously been reported across the 20-cm depth horizon for this site and attributed to a transition from oxic to anoxic bottom water that occurred ~350 years BP. However, we show that this horizon also coincides with a boundary between the base of a hemipelagic mud section and the top of a turbidite interval, complicating the interpretation of organic geochemical data across this boundary. Radiocarbon signatures of DIC diffusing upward into surface sediments indicate that remineralization at depth is supported by relatively ¹⁴C-enriched C_org within the sedimentary matrix. While the exact nature of this C_org is unclear, possible sources are hemipelagic mud sections that were buried rapidly under thick turbidites, and ¹⁴C-rich moieties dispersed within C_org-poor turbidite sections.