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1.
Pore water profiles of Ca, Mg, F, PO4?3 and Mn in the Galapagos Mounds Hydrothermal Field are believed to reflect, in part, upwelling of hydrothermal solutions through the sediments. Concentration-depth profiles in a low heat flow area just north of the Mounds Field display diagenetic changes typical of those found in pore waters underlying highly productive surface waters, consistent with the inference of no water flow or very slow downwelling (w < 5 cm/yr) of bottom water through these sediments. Rates of upward advection calculated from Mounds Field pore water profiles of Ca, Mg, and F profiles agree well with each other, averaging about 1 cm/yr in the pelagic sediments near the mounds and 15–30 cm/yr within the hydrothermal mounds themselves. The upward advection also modifies the shape of PO4?3 and Mn profiles.Advection rates inferred from the pore water data are generally in reasonable agreement with those made from heat flow data.The higher Ca and lower Mg, F, PO4?3 and Mn concentrations in Mounds Field pore waters (compared with those of the low heat flow area) suggest chemical exchange between the solution and basalt prior to upwelling. Li+, K+, Rb+, Sr++ and SO4? concentrations are indistinguishable from bottom water. This suggests very high effective water/rock ratios during the reactions which produced the upwelling solutions, perhaps due to extensive prior alteration of basalt adjacent to the flow path of water through the crust Inferred reaction temperatures are between 70–150°C.  相似文献   

2.
A series of seasonal cores was taken in a high marsh near the terminus of Delaware Bay, U.S.A. A seasonal harmonic diffusion model was successfully fit to the concentration profiles of chloride ion in the salt marsh pore waters yielding a calculated sedimentary diffusion coefficient.Virtually all other chemical reactions within salt marsh sediments are directly linked to the rate and stoichiometry of organic decomposition. The rich organic input from the grass Spartina alterniflora is oxidized anaerobically through the process of sulfate reduction. Over 90% of this net decomposition of organic matter takes place in the uppermost 20 cm. The model for sulfate reduction proposed yields an internally consistent set of both pore water (HCO?3, NH+4, HPO2?4, HS?, SO2?4) and solid phase (FeS2) distribution profiles for these sediments. Steady state assumptions and the use of mean annual constants can be employed to model the net rates of diagenetic processes in salt marshes. The pore water concentrations of sulfate ion as well as those ions released by sulfate reduction (HCO?3, NH+4, HPO2?4, HS?) are modeled by a system composed of an upper zone, where extensive reconsumption of these metabolite ions occurs, and a lower zone where steady state production and no ion reconsumption occurs.A major product of the sulfate reduction is pyrite, whose accumulation rate is greatest between 7 and 9 cm depth, where it equals the net rate of sulfate reduction. Above this zone little pyrite accumulates due to extensive reoxidation. Below 9 cm the rate of pyritization is controlled by the rate of sulfidation of a refractory iron phase.  相似文献   

3.
Fixed-ammonium in clays associated with crude oils   总被引：3，自引：0，他引：3  
The association of ammonium (NH4+) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH4 in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH4-substitution occurs near mature hydrocarbons. Results show higher fixed-NH4 concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH4 concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH4 in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.Tmax = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH4 averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH4-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.Tmax = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH3 during crude oil generation or migration is recorded byNH4+ substitution in clays.Fixed-NH4 and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH4+ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH4+ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.  相似文献   

4.
We examined the effects of seasonal salinity changes on sediment ammonium (NH4 +) adsorption and exchange across the sediment–water interface in the Parker River Estuary, by means of seasonal field sampling, laboratory adsorption experiments, and modeling. The fraction of dissolved NH4 + relative to adsorbed NH4 + in oligohaline sediments rose significantly with increased pore water salinity over the season. Laboratory experiments demonstrated that small (∼3) increases in salinity from freshwater conditions had the greatest effect on NH4 + adsorption by reducing the exchangeable pool from 69% to 14% of the total NH4 + in the upper estuary sediments that experience large (0–20) seasonal salinity shifts. NH4 + dynamics did not appear to be significantly affected by salinity in sediments of the lower estuary where salinities under 10 were not measured. We further assessed the importance of salinity-mediated desorption by constructing a simple mechanistic numerical model for pore water chloride and NH4 + diffusion for sediments of the upper estuary. The model predicted pore water salinity and NH4 + profiles that fit measured profiles very well and described a seasonal pattern of NH4 + flux from the sediment that was significantly affected by salinity. The model demonstrated that changes in salinity on several timescales (tidally, seasonally, and annually) can significantly alter the magnitude and timing of NH4 + release from the sediments. Salinity-mediated desorption and fluxes of NH4 + from sediments in the upper estuary can be of similar magnitude to rates of organic nitrogen mineralization and may therefore be important in supporting estuarine productivity when watershed inputs of N are low.  相似文献   

5.
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.  相似文献   

6.
Biologically available nitrogen (fixed N) is removed from the oceans by metabolic conversion of inorganic N forms (nitrate and ammonium) to N2 gas. Much of this removal occurs in marine sediments, where reaction rates are thought to be limited by diffusion. We measured the concentration and isotopic composition of major dissolved nitrogen species in anoxic sediments off the coast of California. At depths below the diffusive penetration of nitrate, we found evidence of a large nitrate pool transported into the sediments by motile microorganisms. A ∼20‰ enrichment in 15N and 18O of this biologically transported nitrate over bottom water values and elevated [N2] and δ15N-N2 at depth indicate that this nitrate is consumed by enzymatic redox reactions with the production of N2 as the end product. Elevated N2O concentrations in pore waters below the nitrate diffusion depth confirm that these reactions include the denitrification pathway. A data-constrained model shows that at least 31% of the total N2 production in anoxic sediments is linked to nitrate bio-transport. Under suboxic/anoxic regimes, this nitrate bio-transport augments diffusive transport, thus increasing benthic fixed nitrogen losses and the reducing burial efficiency of sedimentary organic matter.  相似文献   

7.
Quantifying Sediment Nitrogen Releases Associated with Estuarine Dredging   总被引：1，自引：0，他引：1  
Experimental studies of sediment pore water NH4 + chemistry, adsorbed NH4 + concentrations, sediment?Cwater NH4 + exchange and N2?CN flux were carried out to quantify the mass of labile N that can be released during large-scale dredging activities. Pore water NH4 + concentrations below 0.5-m sediment depth averaged 5 ± 2 mmol L?1 with average adsorbed NH4 + concentrations of 11 ??mol g?1. Elevated NH4 + concentrations found in rapidly accreting dredge channels are partly a result of the rapid advective burial of both reactive organic matter and pore water. Elutriate tests, a dilution of sediment with site water, yielded adsorbed NH4 + concentrations very similar to those using the more typical KCl extraction. Intact deep sediment sections exposed to overlying water, used to simulate postdredging conditions, showed high initial fluxes of ammonium and no development of coupled nitrification?Cdenitrification under the cold incubation conditions. Despite high concentrations and effluxes of NH4 + during dredging, the amount of NH4 + release during dredging was <0.5% of northern Chesapeake Bay sediment fluxes. The likelihood of large environmental effects of nitrogen release during the dredging of navigational channels in the Chesapeake Bay is low.  相似文献   

8.
G. P. Glasby  K. Notsu   《Ore Geology Reviews》2003,23(3-4):299-339
The Okinawa Trough is a heavily sedimented, rifted back-arc basin formed in an intracontinental rift zone. Submarine hydrothermal activity is located within the six back-arc rifts located in the middle and southern Okinawa Trough and its distribution is controlled principally by tectonic factors. Subduction of the Daito and Gagua Ridges beneath the Ryukyu Arc has resulted in fracturing of the brittle lithosphere beneath the Okinawa Trough. Hydrothermal activity is strongest in the volcanic arc-rift migration phenomenon (VAMP) area plus the JADE site and Southernmost Part of the Okinawa Trough (SPOT) area which form the prolongation of these two ridges. These areas are characterized by extremely high heat flow locally. Submarine hydrothermal fluids from the Okinawa Trough tend to be strongly influenced by interaction of the hydrothermal fluids with organic matter in the sediment resulting in high alkalinity and NH4+ concentrations of the fluids. The fluids also contain high concentrations of CO2 of magmatic origin. Submarine hydrothermal mineralization in the trough is diverse. The CLAM site consists principally of carbonate chimneys. Interaction of the hydrothermal fluid with organic matter in the sediment is particularly strong at this site. This is most probably a sediment-hosted deposit in which sulphide minerals have deposited within the sediment column leaving ‘spent ore-fluids’ to emerge at the seafloor. The JADE site consists of active and inactive sulphide–sulphate chimneys and mounds. The Zn–Pb-rich sulphides at this site contain the highest concentrations of Pb, Ag and Au so far recorded in submarine hydrothermal sulphide deposits. At Minami-Ensei Knoll and Hatoma Knoll, active and inactive chimneys consist principally of anhydrite and barite as a result of phase separation of the hydrothermal fluids beneath the seafloor. An intense black smoker has recently been discovered at Yonaguni Knoll in the SPOT area. If it is confirmed that sulphide mineralization is dominant at this site, this could be a highly prospective area. The most prospective areas for economic-grade minerals in the Okinawa Trough appear to be the JADE site and the SPOT area.  相似文献   

9.
Hydrogen cyanide is an excellent organic reagent and is central to most of the reaction pathways leading to abiotic formation of simple organic compounds containing nitrogen, such as amino acids, purines and pyrimidines. Reduced carbon and nitrogen precursor compounds for the synthesis of HCN may be formed under off-axis hydrothermal conditions in oceanic lithosphere in the presence of native Fe and Ni and are adsorbed on authigenic layer silicates and zeolites. The native metals as well as the molecular hydrogen reducing CO2 to CO/CH4 and NO3 -/NO2 - to NH3/NH4 + are a result of serpentinization of mafic rocks. Oceanic plates are conveyor belts of reduced carbon and nitrogen compounds from the off-axis hydrothermal environments to the subduction zones, where compaction, dehydration, desiccation and diagenetic reactions affect the organic precursors. CO/CH4 and NH3/NH4 + in fluids distilled out of layer silicates and zeolites in the subducting plate at an early stage of subduction will react upon heating and form HCN, which is then available for further organic reactions to, for instance, carbohydrates, nucleosides or even nucleotides, under alkaline conditions in hydrated mantle rocks of the overriding plate. Convergent margins in the initial phase of subduction must, therefore, be considered the most potent sites for prebiotic reactions on Earth. This means that origin of life processes are, perhaps, only possible on planets where some kind of plate tectonics occur.  相似文献   

10.
The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions. In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca2+, Mg2+ and Sr2+ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition. Stratigraphic analysis and δ13C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr?1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.  相似文献   

11.
Despite its location on sediment-free basalt, vent fluids from the Main Endeavour Field (MEF) contain chemical species that indicate fluids have interacted with sediments during circulation. We report on the distribution and isotopic abundances of organic compounds (C1-C3 alkanes and alkenes, benzene and toluene) in fluids collected from the Main Endeavour Field (MEF) in July, 2000, to understand the processes that regulate their abundances and characterize fluid sources. Aqueous organic compounds are derived from the thermal alteration of sedimentary organic matter and subsequently undergo further oxidation reactions during fluid flow. Fluid:sediment mass ratios calculated using ΣNH4 concentrations indicate that the sediments are distal to the MEF, resulting in a common reservoir of fluids for all of the vents. Following the generation from sediment alteration, aqueous organic compounds undergo secondary alteration reactions via a stepwise oxidation reaction mechanism. Alkane distributions and isotopic compositions indicate that organic compounds in MEF fluids have undergone a greater extent of alteration as compared to Middle Valley fluids, either due to differences in subsurface redox conditions or the residence time of fluids at subsurface conditions. The distributions of the aromatic compounds benzene and toluene are qualitatively consistent with the subsurface conditions indicated by equilibration of aqueous alkanes and alkanes. However, benzene and toluene do not achieve chemical equilibrium in the subsurface. Methane and CO2 also do not equilibrate chemically or isotopically at reaction zone temperatures, a likely result of an insufficient reaction time after addition of CO2 from magmatic sources during upflow. The organic geochemistry supports the assumption that the sediments with which MEF fluids interact has the same composition as sediments present in Middle Valley itself, and highlight differences in subsurface reaction zone conditions and fluid flow pathways at these two sites.  相似文献   

12.
热液烃的生成与深部油气藏   总被引：25，自引：1，他引：25  
热液烃不仅分布于洋底,在大陆也有广泛分布,实验表明:热液对碳酸盐岩和沉积有机质的作用均有油气生成;洋底火山岩流体包裹体、原油、有机质Pb、Sr、Nd同位素均表明地幔流体在油气生成中的作用。认识热液烃的存在对开拓深部油气藏的勘探有重要意义。  相似文献   

13.
Through the Deep Sea Drilling Project samples of interstitial solutions of deeply buried marine sediments throughout the World Ocean have been obtained and analyzed. The studies have shown that in all but the most slowly deposited sediments pore fluids exhibit changes in composition upon burial. These changes can be grouped into a few consistent patterns that facilitate identification of the diagenetic reactions occurring in the sediments.Pelagic clays and slowly deposited (<1 cm/103yr) biogenic sediments are the only types that exhibit little evidence of reaction in the pore waters.In most biogenic sediments sea water undergoes considerable alteration. In sediments deposited at rates up to a few cm/103 yr the changes chiefly involve gains of Ca2+ and Sr2+ and losses of Mg2+ which balance the Ca2+ enrichment. The Ca-Mg substitution may often reach 30 mM/kg while Sr2+ may be enriched 15-fold over sea water. These changes reflect recrystallization of biogenic calcite and the substitution of Mg2+ for Ca2+ during this reaction. The Ca-Mg-carbonate formed is most likely a dolomitic phase. A related but more complex pattern is found in carbonate sediments deposited at somewhat greater rates. Ca2+ and Sr2+ enrichment is again characteristic, but Mg2+ losses exceed Ca2+ gains with the excess being balanced by SO4post staggered2? losses. The data indicate that the reactions are similar to those noted above, except that the Ca2+ released is not kept in solution but is precipitated by the HCO3post staggered? produced in SO4post staggered2? reduction. In both these types of pore waters Na+ is usually conservative, but K+ depletions are frequent.In several partly consolidated sediment sections approaching igneous basement contact, very marked interstitial calcium enrichment has been found (to 5.5 g/kg). These phenomena are marked by pronounced depletion in Na+, Si and CO2, and slight enhancement in Cl?. The changes are attributed to exchange of Na+ for Ca2+ in silicate minerals forming from submarine weathering of igneous rocks such as basalts. Water is also consumed in these reactions, accounting for minor increases in total interstitial salinity.Terrigenous, organic-rich sediments deposited rapidly along continental margins also exhibit significant evidences of alteration. Microbial reactions involving organic matter lead to complete removal of SO4post staggered2?, strong HCO3post staggered? enrichment, formation of NH4post staggered+, and methane synthesis from H2 and CO2 once SO4post staggered2? is eliminated. K+ and often Na+ (slightly) are depleted in the interstitial waters. Ca2+ depletion may occur owing to precipitation of CaCO3. In most cases interstitial Cl? remains relatively constant, but increases are noted over evaporitic strata, and decreases in interstitial Cl? are observed in some sediments adjacent to continents.  相似文献   

14.
Organic matter was experimentally extracted by supercritical fluids(CO2 1% isopropanol)from petroleum source rocks of different thermo-maturities at different buried depths in the same stratigraphic unit in the Dongying Basin.The results show that supercritical fluid extraction(SFE)is more effective than Soxhlet extraction(SE),with higher amounts and greater varieties of hydrocarbons and soluble organic matter becoming extractive.The supercritical CO2 extraction is therefore considered more valuable in evaluation of petroleum source rocks and oil resources,particularly those of immature types.  相似文献   

15.
Organogenic sediments (sapropels) in lakes are characterized by a reduced type of diagenesis, during which organic compounds are decomposed, the chemical composition of the pore waters is modified, and authigenic minerals (first of all, pyrite) are formed. Pyrolysis data indicate that organic matter undergoes radical transformatons already in the uppermost sapropel layers, and the composition of this organic matter is principally different from the composition of the organic matter of the its producers. The sapropels contain kerogen, whose macromolecular structure starts to develop during the very early stages of diagenesis, in the horizon of unconsolidated sediment (0–5 cm). The main role in the diagenetic transformations of organic matter in sediments is played by various physiological groups of microorganisms, first of all, heterotrophic, which amonifying, and sulfate-reducing bacteria. SO42? and Fe2+ concentrations in the pore waters of the sediments are determined to decrease (because of bacterial sulfate reduction), while concentrations of reduced Fe and S species (pyrite) in the solid phase of the sediment, conversely, increase. Comparative analysis shows that, unlike sapropels in lakes in the Baikal area, sapropels in southern West Siberia are affected by more active sulfate reduction, which can depend on both the composition of the organic matter and the SO42? concentration in the pore waters.  相似文献   

16.
A comprehensive study of authigenic carbonates and associated fauna in Late Albian organic‐rich, deep‐water deposits (the Black Flysch Group) reveals that carbonate precipitation was a by‐product of the anaerobic oxidation of hydrocarbon‐rich hydrothermal fluids. The authigenic carbonates are exposed along the Kardala and Alkolea sea cliffs in the western Pyrenees. The two vent carbonates occur 1 km apart adjacent to the synsedimentary, right‐reverse Mutriku fault, but in contrasting structural domains: the Kardala carbonates occur on a structural ridge (hangingwall) and the Alkolea carbonates are positioned at the base of an erosional scarp (folded downward footwall). The similarity in pattern of the carbonate phases and complex paragenetic events for both vent precipitates implies that hydrothermal fluid generation processes and pore‐water evolution during early and late diagenesis were similar. Nevertheless, a comparison of the geochemistry, fossil fauna and morphology of carbonate structures of both precipitates suggests that the vented hydrocarbon type, flow intensity and temperature of hydrothermal fluids were different. At the Kardala vent, intense focused flow of hot (up to 109 °C), oil‐rich fluids were generated, allowing the development of a relatively abundant chemosynthesis‐based fauna. In contrast, at the Alkolea vent, diffuse flows of warm, thermogenic methane‐rich fluids were expelled to the sea floor and no chemosynthetic fauna developed. These differences are related to the contrasting structural setting of each locality. Similar δ13Corg values for both pyrobitumen‐fills and host unit organic matter suggest that the hydrocarbon source was the Black Flysch Group. Contact alteration of these organic‐rich sediments by syndepositional hydrothermal fluids generated hydrothermal petroleum (oil and gas hydrocarbons) which probably migrated updip to the sea floor by contemporary compression tectonics.  相似文献   

17.
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18.
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.  相似文献   

19.
Berner (1971) has solved the differential equation governing the concentration in interstitial water of substances produced or consumed during steady-state diagenesis. We have shown that closed solutions exist for non-steady-state diagenesis as well, and that these solutions are best obtained by means of Green's functions. Non-uniform distribution of decomposable organic matter in sediments is a major cause of non-steady-state diagenesis. However, the effect of such non-uniform distributions on the composition of interstitial water in sediments is pronounced only when the rate of deposition exceeds ca. 200 cm/1000 yr. At slower deposition rates, diffusion is sufficiently rapid to damp out major fluctuations in the concentration of ions such as SO2?4, NH+4, PO3?4, and HCO?3. Concentration profiles of these ions therefore tend to be similar to steady-state profiles even if the concentration of decomposable organic matter is quite heterogeneous.The concentration of SO2?4 frequently approaches 0 in marine sediments rich in decomposable organic matter. In such sediments the total quantity of SO2?4 reduced during diagenesis is proportional to the concentration of SO2?4 in sea water even if the bacterial rate of decomposition of organic matter is nearly independent of the SO2?4 concentration in interstitial water. This implies that the rate of SO2?4 removal from sea water by reduction to sulfide is roughly proportional to the sulfate concentration in seawater.Solutions for the diagenetic equation exist for reasonable variations of the rate of ionic diffusion in interstitial waters and for changes in the rate of deposition due to compaction.  相似文献   

20.
We used fine-scale porewater profiles and rate measurements together with a multiple component transport–reaction model to investigate carbon degradation pathways and the coupling between electron and proton transfer reactions in Lake Champlain sediments. We measured porewater profiles of O2, Mn2+, Fe2+, HS−, pH and pCO2 at mm resolution by microelectrodes, and profiles of NO3 −, SO4 2−, NH4 +, total inorganic carbon (DIC) and total alkalinity (TA) at cm resolution using standard wet chemical techniques. In addition, sediment–water fluxes of oxygen, DIC, nitrate, ammonium and N2 were measured. Rates of gross and net sulfate reduction were also measured in the sediments. It is shown that organic matter (OM) decomposes via six pathways: oxic respiration (35.2%), denitrification (10.4%), MnO2 reduction (3.6%), FeOOH reduction (9.6%), sulfate reduction (14.9%), and methanogenesis (26.4%). In the lake sediments, about half of the benthic O2 flux is used for aerobic respiration, and the rest is used for the regeneration of other electron acceptors produced during the above diagenetic reactions. There is a strong coupling between O2 usage and Mn2+ oxidation. MnO2 is also an important player in Fe and S cycles and in pH and TA balance. Although nitrate concentrations in the overlying water were low, denitrification becomes a quantitatively important pathway for OM decomposition due to the oxidation of NH4 + to NO3 −. Finally, despite its low concentration in freshwater, sulfate is an important electron acceptor due to its high efficiency of internal cycling. This paper also discusses quantitatively the relationship between redox reactions and the porewater pH values. It is demonstrated here that pH and pCO2 are sensitive variables that reflect various oxidation and precipitation reactions in porewater, while DIC and TA profiles provide effective constraints on the rates of various diagenetic reactions.  相似文献   

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