Early carbonate diagenesis in slope sequences and at their boundaries, Cenozoic, offshore New Jersey (ODP Leg 150)

This paper reports the genetic links among the depth distribution, mineralogy, and stable isotopic composition of diagenetic carbonates with sedimentation rates and types and preservation of organic matter in the terrigenous and biogenic sediments of Oligocene and Miocene age on the New Jersey slope. Calcites formed close to the sediment surface at sequence boundaries and maximum flooding surfaces, when the profile of early-diagenetic reactions was stabilized in the sediment column for extended periods. Dolomites precipitated in the sulfate reduction zone when diagenetic profiles stabilized during truncation, sequence boundary formation, and the deposition of lowstand sediments that overlie the sequence boundaries. Most dolomites occur in distal slope sediments that were deposited before the shelf had prograded into the study area. Siderites formed during a later stage of burial in the methanogenic zone; they are not directly genetically related to the sequence stratigraphy of the New Jersey slope. The diagene-tic dolomites and siderites occur in widely separated depth intervals below the present sea floor. The distribution of the diagenetic carbonates and their preferential occurrence in separated depth intervals resulted from different combinations of sedimentation rates and organic matter types and preservation.     

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ¹³C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in ¹³C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate-methane transition zone 6-7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.     

沉积过程对自生黄铁矿硫同位素的约束

自生黄铁矿是海洋沉积物中还原态硫的主要赋存形式,其形成过程与有机质矿化相关,影响全球的C-S-Fe生物地球化学循环。自生黄铁矿硫同位素分馏主要受微生物硫酸盐还原的控制,但近期的研究成果表明局部沉积环境的改变也可以影响黄铁矿硫同位素的组成,特别是在浅海环境。在浅海非稳态沉积环境内,物理再改造和生物扰动作用,导致硫酸盐还原带内生成的硫化物被再氧化,进而影响黄铁矿的硫同位素值。浅海沉积过程容易受到古气候和海平面变化的影响,引起沉积速率的剧烈波动,导致有机质和活性铁输入的不稳定,进而影响成岩系统的开放性和硫酸盐还原速率,最终影响黄铁矿的硫同位素值。另外,沉积速率的改变还影响硫酸盐—甲烷转换带的迁移,造成有机质和甲烷厌氧氧化硫酸盐还原的相互转化,产生不同的硫同位素信号。东海内陆架泥质区为研究沉积过程对自生黄铁矿的形成及其硫同位素组成的约束机制提供了很好的研究材料。该区域有很好的沉积学研究基础,自生黄铁矿丰富、并且个别层位有生物气（甲烷为主）存在,是研究边缘海C-S-Fe循环的理想场所。     

A theoretical model of the stable sulfur isotope distribution in marine sediments

A diffusion-diagenesis model of the sulfur cycle is developed to calculate theoretical distributions of stable sulfur isotopes in marine sediments. The model describes the depth variation in δ³⁴S of dissolved sulfate and H₂S. and of pyrite. The effects of sulfate reduction, sulfate and H₂S diffusion. and of sedimentation are considered as well as the bacterial isotope fractionation and the degree of pyrite formation. Under open system conditions of sulfur diagenesis the isotopic difference, ΔSO^2?₄ — H₂S, tends to increase with depth being smaller than the bacterial fractionation factor near the sediment surface and larger in deeper layers. The two isotopes in SO^2?₄ or in H₂S do not diffuse in the same proportion as they occur in the porewater. This explains why sulfur, which is incorporated from seawater sulfate by diffusion and precipitation as pyrite, can be enriched in ³²S relative to the seawater sulfate. The model calculations demonstrate the importance of taking the whole dynamic sulfur cycle into account before drawing conclusions about sulfur diagenesis from the stable isotope distribution.     

The Impact of Sediment and Carbon Fluxes on the Biogeochemistry of Methane and Sulfur in Littoral Baltic Sea Sediments (Himmerfjärden, Sweden)

Three sediment stations in Himmerfjärden estuary (Baltic Sea, Sweden) were sampled in May 2009 and June 2010 to test how low salinity (5–7 ‰), high primary productivity partially induced by nutrient input from an upstream waste water treatment plant, and high overall sedimentation rates impact the sedimentary cycling of methane and sulfur. Rates of sediment accumulation determined using ²¹⁰Pb_excess and ¹³⁷Cs were very high (0.65–0.95 cm?year^?1), as were the corresponding rates of organic matter accumulation (8.9–9.5 mol C?m^?2?year^?1) at all three sites. Dissolved sulfate penetrated <20 cm below the sediment surface. Although measured rates of bicarbonate methanogenesis integrated over 1 m depth were low (0.96–1.09 mol?m^?2?year^?1), methane concentrations increased to >2 mmol?L^?1 below the sulfate–methane transition. A steep gradient of methane through the entire sulfate zone led to upward (diffusive and bio-irrigative) fluxes of 0.32 to 0.78 mol?m^?2?year^?1 methane to the sediment–water interface. Areal rates of sulfate reduction (1.46–1.92 mol?m^?2?year^?1) integrated over the upper 0–14 cm of sediment appeared to be limited by the restricted diffusive supply of sulfate, low bio-irrigation (α?=?2.8–3.1 year^?1), and limited residence time of the sedimentary organic carbon in the sulfate zone. A large fraction of reduced sulfur as pyrite and organic-bound sulfur was buried and thus escaped reoxidation in the surface sediment. The presence of ferrous iron in the pore water (with concentrations up to 110 μM) suggests that iron reduction plays an important role in surface sediments, as well as in sediment layers deep below the sulfate–methane transition. We conclude that high rates of sediment accumulation and shallow sulfate penetration are the master variables for biogeochemistry of methane and sulfur cycling; in particular, they may significantly allow for release of methane into the water column in the Himmerfjärden estuary.     

Biogeochemical processes involving acetate in sub-seafloor sediments from the Bering Sea shelf break

Biogeochemical processes involving acetate in sub-seafloor sediments from piston core PC23B from the Bering Sea shelf break were inferred by examining the stable carbon isotopic relationships between acetate and other relevant carbon compounds: total organic carbon (TOC) in the sediment solid phase, and dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) in pore water. Throughout the core, the isotopic composition of acetate (δ¹³C_acetate), from −31‰ to −29‰, was ¹³C-depleted by ca. 7‰ vs. DOC (δ¹³C_DOC) and its depth profile approximately paralleled that of δ¹³C_DOC, suggesting that the principal process producing acetate was fermentation of dissolved organic compounds. However, the ¹³C depletion in δ¹³C_acetate indicates some contribution of acetogenesis to total acetate production, because acetogenesis results in ¹³C depletion of the acetate produced. The relative contribution of acetogenesis via the H₂/CO₂ reaction, calculated by using a two source isotope mixing model, increased with depth in the sulfate reduction zone from 10% to 15% and was constant at 19% in the methanogenic zone. The acetogenic contribution to acetate production in the methanogenic zone underlying the sulfate reduction zone is consistent with reported observations, whereas the occurrence of acetogenesis in the sulfate reduction zone may be related to the contribution of terrestrial organic matter (OM) to the sedimentary OM in that depth interval, because the terrestrial component likely includes precursors that favor organoautotrophic acetogenesis. The high acetate concentration (up to 81 μM) and TOC content (up to 1.4%) at the same depth (<200 cmbsf) suggest that some relationship exists between acetate production rate and TOC content, or that a temperature increase during core storage at room temperature might stimulate acetate-producing microbial activity in the high TOC sediment.     

Reconstruction of the Holocene climate based on a carbonate sedimentary record from shallow saline Lake Verkhnee Beloe (western Transbaikalia)

We present results of mineralogical and crystallochemical studies of the Holocene carbonate sediments of a small saline lake localized in the Borgoi dry-steppe region, western Transbaikalia. Mg-calcites with a varying Mg content are predominant in the assemblage of endogenic carbonate minerals from bottom sediments. Mathematical modeling of the XRD spectra of carbonates permitted us to identify excess-Ca dolomites, which are an indicator of a shallow (playa) lake. The studies showed that the lacustrine Mg-calcites do not form a continuous series from low- to high-Mg varieties. We discuss the cause of this phenomenon and also consider the existing viewpoints of the structure of low-temperature Mg-calcites and excess-Ca dolomites and their formation conditions in lacustrine sediments. Juxtaposing the carbonate record with the data of lithological analysis, determined stable isotopes (δ¹⁸O and δ¹³C), and distribution of some geochemical indicators of climatic changes, we reconstructed the intricate evolution of Lake Verkhnee Beloe, which was controlled by the regional climate since the postglacial period till the present day.     

海湾水库蓄水初期的单次往复密度流

为了探讨海湾水库蓄水初期单次往复水平密度流的产生与效应,进行砂质斜坡沉积物与水体之间盐分交换的水槽实验。通过沉积物孔隙水与其上覆水的多剖面电导率动态监测,分析盐分的时空分布特征,并计算深水区、浅水区和中心区的边界层单位面积含盐总量。实验结果显示,进水在浅水区沉积物表面产生明显的渗入-溢出现象,浅水区沉积物孔隙水盐分浓度显著低于中心区与深水区同一高度的盐分浓度,深水区初始底边界层含盐量与初始边界层下边界盐分浓度均为最高;这表明进水过程在倾斜沉积物表面产生了前进密度流,水流携带的盐分在坡底累积。水槽进满水后深水区边界层含盐总量与边界层下边界盐分浓度快速降低,并且浅水区表层沉积物孔隙水与深水区同一深度水体之间的盐分快速达到平衡;这表明蓄水初期在两者之间形成了返回密度流,从浅水区表层沉积物冲刷出的盐分在密度流作用下再次进入沉积物。为避免再次进入沉积物的盐分在后期继续影响水库泛咸,建议在蓄水结束后尽快实施坡底咸水排除方案。     

Hydrochemistry,origin and evolution of sedimentary subsurface fluids: II. Early diagenetic pore-water evolution in high sedimentation-rate offshore basins

High sedimentation-rate basins are characteristic of the continental margins, where sedimentation rates up to 500m/Ma and more are no exception. The sediments are rich in organic matter and undergo a well-established sequence of bacterial oxidation reactions, starting at the sediment/water interface with: (1) the oxidation zone (absent in euxinic basins), which is followed downwards by (2) the nitrate reduction zone, (3) the sulfate reduction zone, (4) the carbonate reduction zone, (5) the fermentation zone and (6) the decarboxylation zone, which marks the onset of thermocatalytic reactions characteristic of the intermediate stage (and deeper stages) of diagenesis. This sequence of bacterially mediated organic-matter decomposition reactions in rapidly deposited sediments on the continental margins is well reflected in the vertical trends of pore-water chemistry. Carbon isotopic fractionation permits to distinguish between zones (1) to (3) with negative δ¹³C values for the CO₂ generated, and between zones (4) and (5) with increasingly heavier carbon-isotopes in CO₂ (up to + 15 to + 25‰ δ¹³C). The formation of gas-hydrates causes characteristic chemical and isotopic signatures in pore waters retrieved from hydrate-bearing sediments. After hydrate decomposition (in the sampling process or at the base of hydrate zones) marked chlorimity decreases accompanied by increases in heavy oxygen isotopes are observed. These are distinctly different from the effects of meteoric water influx, which are not accompanied by positive δ¹⁸O values. The opposite trend of increasing salinity at shallow burial depths, rather than pore-waters freshening, is observed in the vicinity of evaporites.     

Sulfur biogeochemistry and isotopic fractionation in shallow groundwater and sediments of Owens Dry Lake, California

Groundwater and sediment samples (∼ 1 m depth) at sites representative of different groundwater pathways were collected to determine the aqueous speciation of sulfur and the fractionation of sulfur isotopes in aqueous and solid phases. In addition, selected sediment samples at 5 depths (from oxic to anoxic layers) were collected to investigate the processes controlling sulfur biogeochemistry in sedimentary layers. Pyrite was the dominant sulfur-bearing phase in the capillary fringe and groundwater zones where anoxic conditions are found. Low concentrations of pyrite (< 5.9 g kg^− 1) coupled with high concentrations of dissolved sulfide (4.81 to 134.7 mg L^− 1) and low concentrations of dissolved Fe (generally < 1 mg L^− 1) and reducible solid-phase Fe indicate that availability of reactive Fe limits pyrite formation. The relative uniformity of down-core isotopic trends for sulfur-bearing mineral phases in the sedimentary layers suggests that sulfate reduction does not result in significant sulfate depletion in the sediment. Sulfate availability in the deeper sediments may be enhanced by convective vertical mixing between upper and lower sedimentary layers due to evaporative concentration. The large isotope fractionation between dissolved sulfate and sedimentary sulfides at Owens Lake provides evidence for initial fractionation from bacterial sulfate reduction and additional fractionation generated by sulfide oxidation followed by disproportionation of intermediate oxidation state sulfur compounds. The high salinity in the Owens Lake brines may be a factor controlling sulfate reduction and disproportionation in hypersaline conditions and results in relatively constant values for isotope fractionation between dissolved sulfate and total reduced sulfur.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): I. Geochemical and microbiological analyses

The organic rich sediments of the Skagerrak contain high quantities of shallow gas of mostly biogenic origin that is transported to the sediment surface by diffusion. The sulfate methane transition zone (SMTZ), where anaerobic oxidation of methane (AOM) and sulfate reduction occur, functions as a methane barrier for this upward diffusing methane.To investigate the regulation of AOM and sulfate reduction rates (SRR) and the controls on the efficiency of methane consumption, pore water concentrations, and microbial rates of AOM, sulfate reduction and methanogenesis were determined in three gravity cores collected along the slope of the Norwegian Trench in the Skagerrak. SRR occurred in two distinct peaks, at the sediment surface and the SMTZ, the latter often exceeding the peak AOM rates that occurred at the bottom of the SMTZ. Highest rates of both AOM and SRR were observed in a core from a pockmark, where advective methane transport occurred, generating high methane and sulfate fluxes. But even at this site with a shallow SMTZ, the entire flux of methane was oxidized below the sediment surface. AOM, SRR and methanogenesis seem to be closely associated and strongly regulated by sulfate concentrations, which were, in turn, regulated by the methane flux. Rate measurements of SRR, AOM and methanogenesis revealed a tight coupling of these processes. Bicarbonate-based methanogenesis occurred at moderate sulfate concentrations (>5 mM) above the AOM zone but seemed to be inhibited in the depth where AOM occurred. The unbalanced stoichiometry of AOM and SRR in the SMTZ was more pronounced in rate measurements than in methane and sulfate fluxes, and seemed more likely be related to enhanced SRR in this zone than an underestimation of methane fluxes.     

Geochemical fingerprints of dolomitization in Bahamian carbonates: Evidence from sulphur,calcium, magnesium and clumped isotopes

In an effort to constrain the mechanism of dolomitization in Neogene dolomites in the Bahamas and improve understanding of the use of chemostratigraphic tracers in shallow‐water carbonate sediments the δ³⁴S, Δ₄₇, δ¹³C, δ¹⁸O, δ^44/40Ca and δ²⁶Mg values and Sr concentrations have been measured in dolomitized intervals from the Clino core, drilled on the margin of Great Bahama Bank and two other cores (Unda and San Salvador) in the Bahamas. The Unda and San Salvador cores have massively dolomitized intervals that have carbonate associated sulphate δ³⁴S values similar to those found in contemporaneous seawater and δ^44/40Ca, δ²⁶Mg values, Sr contents and Δ₄₇ temperatures (25 to 30°C) indicating relatively shallow dolomitization in a fluid‐buffered system. In contrast, dolomitized intervals in the Clino core have elevated values of carbonate associated sulphate δ³⁴S values indicating dolomitization in a more sediment‐buffered diagenetic system where bacterial sulphate reduction enriches the residual in ³⁴S, consistent with high sediment Sr concentrations and low δ^44/40Ca and high δ²⁶Mg values. Only dolomites associated with hardgrounds in the Clino core have carbonate associated δ³⁴S values similar to seawater, indicating continuous flushing of the upper layers of the sediment by seawater during sedimentary hiatuses. This interpretation is supported by changes to more positive δ^44/40Ca values at hardground surfaces. All dolomites, whether they formed in an open fluid‐buffered or closed sediment‐buffered diagenetic system have similar δ²⁶Mg values suggesting that the HMC transformed to dolomite. The clumped isotope derived temperatures in the dolomitized intervals in Clino yield temperatures that are higher than normal, possibly indicating a kinetic isotope effect on dolomite Δ₄₇ values associated with carbonate formation through bacterial sulphate reduction. The findings of this study highlight the utility of applying multiple geochemical proxies to disentangle the diagenetic history of shallow‐water carbonate sediments and caution against simple interpretations of stratigraphic variability in these geochemical proxies as indicating changes in the global geochemical cycling of these elements in seawater.     

The radiocarbon age of organic carbon in marine surface sediments

Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon (¹⁴C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon (¹⁴C_TOC) accumulating in surface sediments we construct a box model that predicts ¹⁴C_TOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that ¹⁴C_TOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed-layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ¹³C_TOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed-layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.     

Polyphosphates as a source of enhanced P fluxes in marine sediments overlain by anoxic waters: Evidence from <Superscript>31</Superscript>P NMR

Sedimentary phosphorus (P) composition was investigated in Effingham Inlet, a fjord located on the west coast of Vancouver Island in Barkley Sound. Solid-state ³¹P nuclear magnetic resonance (NMR) spectroscopy was applied to demineralized sediment samples from sites overlain by oxic and anoxic bottom waters. The two sites were similar in terms of key diagenetic parameters, including the mass accumulation rate, integrated sulfate reduction rate, and bulk sediment organic carbon content. In contrast, P benthic fluxes were much higher at the anoxic site. ³¹P NMR results show that P esters and phosphonates are the major organic P species present at the surface and at depth in sediments at both sites. Polyphosphates were only found in the surface sediment of the site overlain by oxic waters. The varying stability of polyphosphates in microorganisms under different redox conditions may, in part, explain their distribution as well as differences in P flux between the two sites.     

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S⁰ was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H₂S. At the shelf stations, on the other hand, pyrite was significantly depleted in ³⁴S relative to its potential precursors FeS and S⁰. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ³⁴S-values of pyrite down to −38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The ¹⁸O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations.     

The influence of tortuosity on molecular diffusion in freshwater sediments of high porosity

In sediments, diffusive transport of ions and molecules is basically influenced by two sediment characteristics: tortuosity and porosity. For the first time, the formation factor F, which combines the effect of tortuosity and porosity on diffusion, was quantified in freshwater sediments at submillimeter resolution. Sediment cores were treated with KCl and F was determined using a resistivity sensor and K⁺ selective electrodes.F was determined in sediments from different water depths of the eutrophic Lake Zug (Switzerland): In sandy sediments from a shallow site (12 m depth), F increased by approximately 50% within a few millimeters below the sediment surface. In clayey and silty sediments from the oxic (<80 m depth) and seasonally anoxic (80-120 m depth) zones of the lake, the initial increase in F was only 20%. In the permanent anoxic zone (>160 m depth), F increased by only 10% just below the sediment surface. Values of F were correlated with the porosity at each depth. We found close correlations of F = 1.02 · φ^−1.81 for clay-silt sediments, and F = 1.04 · φ^−1.21 for sandy sediments. The exponents are considerably smaller in Lake Zug than found for marine sediments, thus, diffusive transport seems to be less affected by tortuosity in this freshwater system.     

A cryptic sulfur cycle driven by iron in the methane zone of marine sediment (Aarhus Bay, Denmark)

Sulfate reduction and sulfur-iron geochemistry were studied in 5-6 m deep gravity cores of Holocene mud from Aarhus Bay (Denmark). A goal was to understand whether sulfate is generated by re-oxidation of sulfide throughout the sulfate and methane zones, which might explain the abundance of active sulfate reducers deep below the main sulfate zone. Sulfate penetrated down to 130 cm where methane started to build up and where the concentration of free sulfide peaked at 5.5 mM. Below this sulfate-methane transition, sulfide diffused downwards to a sulfidization front at 520 cm depth, below which dissolved iron, Fe²⁺, accumulated in the pore water. Sulfate reduction rates measured by ³⁵S-tracer incubations in the sulfate zone were high due to high concentrations of reactive organic matter. Within the sulfate-methane transition, sulfate reduction was distinctly stimulated by the anaerobic oxidation of methane. In the methane zone below, sulfate remained at positive “background” concentrations of <0.5 mM down to the sulfidization front. Sulfate reduction decreased steeply to rates which at 300-500 cm depth were 0.2-1 pmol SO₄²⁻ cm⁻³ d⁻¹, i.e., 4-5 orders of magnitude lower than rates measured near the sediment surface. The turn-over time of sulfate increased from 3 years at 12 cm depth to 100-1000 years down in the methane zone. Sulfate reduction in the methane zone accounted for only 0.1% of sulfate reduction in the entire sediment column and was apparently limited by the low pore water concentration of sulfate and the low availability of organic substrates. Amendment of the sediment with both sulfate and organic substrates immediately caused a 10- to 40-fold higher, “potential sulfate reduction” which showed that a physiologically intact community of sulfate reducing bacteria was present. The “background” sulfate concentration appears to be generated from the reaction of downwards diffusing sulfide with deeply buried Fe(III) species, such as poorly-reactive iron oxides or iron bound in reactive silicates. The oxidation of sulfide to sulfate in the sulfidic sediment may involve the formation of elemental sulfur and thiosulfate and their further disproportionation to sulfide and sulfate. The net reaction of sulfide and Fe(III) to form pyrite requires an additional oxidant, irrespective of the formation of sulfate. This could be CO₂ which is reduced with H₂ to methane. The methane subsequently diffuses upwards to become re-oxidized at the sulfate-methane transition and thereby removes excess reducing power and enables the formation of excess sulfate. We show here how the combination of these well-established sulfur-iron-carbon reactions may lead to the deep formation of sulfate and drive a cryptic sulfur cycle. The iron-rich post-glacial sediments underlying Holocene marine mud stimulate the strong sub-surface sulfide reoxidation observed in Aarhus Bay and are a result of the glacial to interglacial history of the Baltic Sea area. Yet, processes similar to the ones described here probably occur widespread in marine sediments, in particular along the ocean margins.     

An Experimental Apparatus for Laboratory and Field-Based Perfusion of Sediment Porewater with Dissolved Tracers

The water–sediment interface is a dynamic zone where the benthic and pelagic environments are linked through exchange and recycling of organic matter and nutrients. However, it is often difficult to measure rate processes in this zone. To that end, we designed an experimental apparatus for continuous and homogeneous perfusion of sediment porewater with dissolved conservative (SF₆, Rhodamine WT dye) and isotopic (H¹³CO₃⁻ and ¹⁵NH₄⁺) tracers to study nitrogen and carbon cycling by the sediment microbial community of shallow illuminated sediments. The perfusionator consists of a 60-cm ID × 60-cm high cylinder that includes a reservoir for porewater at the base of the sediment column. Porewater amended with conservative and stable isotopic tracers was pumped through a mixing reservoir and upward through the overlying sediments. We tested the perfusionator in a laboratory setting, as part of an outdoor mesocosm array, and buried in coastal sediments. Conservative and isotopic tracers demonstrated that the porewater tracers were distributed homogeneously through the sediment column in all settings. The perfusionator was designed to introduce dissolved stable isotope tracers but is capable of delivering any dissolved ionic, organic, or gaseous constituent. We see a potentially wide application of this technique in the aquatic and marine sciences in laboratory and field settings.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.     

太湖沉积物中微生物多样性垂向分布特征

运用化学分析方法和PCR-DGGE技术,从沉积物化学及分子生物学角度对太湖沉积物理化性质(pH、Eh)、营养盐及微生物多样性的垂向分布及相关性进行研究。结果表明:沉积物-上覆水接触界面处于轻度还原状态,在表层8.0cm左右以下,Eh随沉积深度的增加迅速下降,还原性逐渐增强,到15.0～22.5cm深度区间内,Eh值基本稳定,还原性最强,之后随深度的进一步增加,Eh呈"之"型缓慢升高。沉积物pH随深度的增加先降低后缓慢升高,pH在整个剖面上变化幅度不大,在7.2～7.6变动。沉积物中含有丰富的营养盐,总氮(TN)、总磷(TP)最高含量分数和有机质(OM)的最高百分比分别为2.436mg/g、0.731mg/g和3.817%,其剖面特征表明,沉积物表层TN和OM远高于底层,其含量随深度增加而降低。TP随着沉积深度的增加呈"之"型缓慢减少。不同深度沉积物的微生物群落呈现出明显的空间分布多样性差异,不同深度沉积物的微生物群落结构之间的相似性和动态性存在差异。多元相关分析结果显示,TN与OM显著相关,理化指标、营养盐中任一指标含量与微生物群落多样性指标之间存在相关性,但不显著,微生物多样性是营养盐及环境物理、化学和生物等多方面共同作用的结果。